title: Self-organization of n-alkane chains in water: length dependent crossover from helix and toroid to molten globule.
abstract: We demonstrate a chain length dependent crossover in the structural properties of linear hydrocarbon (n-alkane) chains using detailed atomistic simulations in explicit water. We identify a number of exotic structures of the polymer chain through energy minimization of representative snapshots collected from molecular dynamics trajectory. While the collapsed state is ring-like (circular) for small chains (CnH2n+2; n<or=20) and spherical for very long ones (n=100), we find the emergence of ordered helical structures at intermediate lengths (n approximately 40). We find different types of disordered helices and toroid-like structures at n=60. We also report a sharp transition in the stability of the collapsed state as a function of the chain length through relevant free energy calculations. While the collapsed state is only marginally metastable for C20H42, a clear bistable free energy surface emerges only when the chain is about 30 monomers long. For n=30, the polymer exhibits an intermittent oscillation between the collapsed and the coil structures, characteristic of two stable states separated by a small barrier.
authors.forename: Suman
authors.initials: S
authors.lastname: Chakrabarty
authors.forename: Biman
authors.initials: B
authors.lastname: Bagchi
mesh_terms: D000473:Alkanes / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D012399:Rotation; D013816:Thermodynamics; D013997:Time Factors; D014867:Water / Q000737:chemistry*
chemical_list: D000473:Alkanes; D014867:Water