Branched versus linear lactide chains for cellulose nanoparticle modification: an atomistic molecular dynamics study.

We studied the structure of brushes consisting of branched oligolactide (OLA) chains grafted onto the surface of cellulose nanoparticles (CNPs) in polylactide (PLA) and compared the outcomes to the case of grafting linear OLA chains using atomistic molecular dynamics simulations. The systems were considered in a melt state. The branched model OLA chains comprised one branching point and three branches, while the linear OLA chains examined had a molecular weight similar to the branched chains. It was shown that free branches of the branched OLA chains tend to fold back toward the CNPs due to dipole-dipole interactions within the grafted layer, in contrast to the well-established behavior of the grafted uncharged branched chains. This result, however, is in qualitative agreement with the conformational behavior known for linear OLA chains. At the same time, no significant difference in the effectiveness of covering the filler surface with grafted branched or linear OLA chains was found. In terms of the expelling ability of the grafted chains and the interaction between PLA and CNP or OLA, the linear chains were broadly similar (sparse grafting) or better (intermediate or dense grafting) compared to the branched ones. Thus, the grafted lactide chains with a linear architecture, rather than their branched counterpart, may be preferable for the covalent modification of cellulose nanoparticles.

Grafting-Induced Structural Ordering of Lactide Chains.

The structure of a grafted layer of lactide chains in the "dry brush" regime immersed in a melt of chemically similar polymer was examined while varying graft lengths. To this end, microsecond atomistic molecular dynamics simulations were performed. Almost no influence of graft length on the fraction of the grafted chains backfolded to the grafting surface was found. However, a structural ordering was unexpectedly observed in the system when the length of the grafted lactide chains was close to approximately 10 Kuhn segments. This ordering of the grafts is characterized by the formation of helical fragments whose structure is in good agreement with the experimental data for the α crystal of the lactide chains. Both the backfolding and the structural ordering may be viewed as the initial stage of the crystallization of the layer of grafted lactide chains. In contrast to the known behavior for conventional polymer brushes in the "dry brush" regime, the structure of the grafted lactide chains can be either amorphous or ordered, depending on the graft length N and the grafting density σ when their product Nσ is fixed.

Unfolding of a comb-like polymer in a poor solvent: translation of macromolecular architecture in the force-deformation spectra.

A numerical self-consistent field modeling approach was employed to study the mechanical unfolding of a globule made by comb-like polymers in a poor solvent with the aim of unraveling how the macromolecular architecture affects the shape of the single-molecule force-deformation curves. We demonstrate that the dependence of the restoring force on the imposed extension of the main chain of the comb-like polymer exhibits a characteristic oscillatory shape in the intermediate deformation range. Theoretical arguments are developed that enable us to relate the shape of the patterns on the force-deformation curves to the molecular architecture (grafting density and length of the side chains) and interaction parameters. Thus, the results of our study suggest a new approach for the determination of macromolecular topology from single-molecule mechanical unfolding experiments.