Molecular dynamics simulations of single-component bottle-brush polymers with flexible backbones under poor solvent conditions

Nikolaos Fytas, P.E. Theodorakis

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    9 Citations (Scopus)

    Abstract

    Conformations of a single-component bottle-brush polymer with a fully flexible backbone under poor solvent conditions are studied by molecular dynamics simulations, using a coarse-grained bead–spring model with side chains of up to N = 40 effective monomers. By variation of the solvent quality and the grafting density σ with which side chains are grafted onto the flexible backbone, we study for backbone lengths of up to Nb = 100 the crossover from the brush/coil regime to the dense collapsed state. At lower temperatures, where collapsed chains with a constant monomer density are observed, the choice of the above parameters does not play any role and it is the total number of monomers that defines the dimensions of the chains. Furthermore, bottle-brush polymers with longer side chains possess higher spherical symmetry compared to polymers with lower side-chain lengths in contrast to what one may intuitively expect, as the stretching of the side chains is less important than the increase of their length. At higher temperatures, always below the Theta (Θ) temperature, coil-like configurations, similar to a single polymer chain, or brush-like configurations, similar to a homogeneous cylindrical bottle-brush polymer with a rigid backbone, are observed, depending on the choice of the particular parameters N and σ. In the crossover regime between the collapsed state (globule) and the coil/brush regime the acylindricity increases, whereas for temperatures outside of this range, bottle-brush polymers maintain a highly cylindrical symmetry in all configurational states.
    Original languageEnglish
    Article number285105
    JournalJournal of Physics Condensed Matter
    Volume25
    Issue number28
    DOIs
    Publication statusPublished - 2013

    Fingerprint

    bottles
    brushes
    Bottles
    Brushes
    Molecular dynamics
    Polymers
    molecular dynamics
    Computer simulation
    polymers
    simulation
    coils
    monomers
    Monomers
    crossovers
    Temperature
    globules
    symmetry
    configurations
    Chain length
    Stretching

    Bibliographical note

    The full text is available free from the link given.

    Keywords

    • soft matter
    • liquids and polymers
    • condensed matter: structural
    • mechanical & thermal
    • chemical physics and physical chemistry

    Cite this

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    title = "Molecular dynamics simulations of single-component bottle-brush polymers with flexible backbones under poor solvent conditions",
    abstract = "Conformations of a single-component bottle-brush polymer with a fully flexible backbone under poor solvent conditions are studied by molecular dynamics simulations, using a coarse-grained bead–spring model with side chains of up to N = 40 effective monomers. By variation of the solvent quality and the grafting density σ with which side chains are grafted onto the flexible backbone, we study for backbone lengths of up to Nb = 100 the crossover from the brush/coil regime to the dense collapsed state. At lower temperatures, where collapsed chains with a constant monomer density are observed, the choice of the above parameters does not play any role and it is the total number of monomers that defines the dimensions of the chains. Furthermore, bottle-brush polymers with longer side chains possess higher spherical symmetry compared to polymers with lower side-chain lengths in contrast to what one may intuitively expect, as the stretching of the side chains is less important than the increase of their length. At higher temperatures, always below the Theta (Θ) temperature, coil-like configurations, similar to a single polymer chain, or brush-like configurations, similar to a homogeneous cylindrical bottle-brush polymer with a rigid backbone, are observed, depending on the choice of the particular parameters N and σ. In the crossover regime between the collapsed state (globule) and the coil/brush regime the acylindricity increases, whereas for temperatures outside of this range, bottle-brush polymers maintain a highly cylindrical symmetry in all configurational states.",
    keywords = "soft matter, liquids and polymers, condensed matter: structural, mechanical & thermal, chemical physics and physical chemistry",
    author = "Nikolaos Fytas and P.E. Theodorakis",
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    T1 - Molecular dynamics simulations of single-component bottle-brush polymers with flexible backbones under poor solvent conditions

    AU - Fytas, Nikolaos

    AU - Theodorakis, P.E.

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    PY - 2013

    Y1 - 2013

    N2 - Conformations of a single-component bottle-brush polymer with a fully flexible backbone under poor solvent conditions are studied by molecular dynamics simulations, using a coarse-grained bead–spring model with side chains of up to N = 40 effective monomers. By variation of the solvent quality and the grafting density σ with which side chains are grafted onto the flexible backbone, we study for backbone lengths of up to Nb = 100 the crossover from the brush/coil regime to the dense collapsed state. At lower temperatures, where collapsed chains with a constant monomer density are observed, the choice of the above parameters does not play any role and it is the total number of monomers that defines the dimensions of the chains. Furthermore, bottle-brush polymers with longer side chains possess higher spherical symmetry compared to polymers with lower side-chain lengths in contrast to what one may intuitively expect, as the stretching of the side chains is less important than the increase of their length. At higher temperatures, always below the Theta (Θ) temperature, coil-like configurations, similar to a single polymer chain, or brush-like configurations, similar to a homogeneous cylindrical bottle-brush polymer with a rigid backbone, are observed, depending on the choice of the particular parameters N and σ. In the crossover regime between the collapsed state (globule) and the coil/brush regime the acylindricity increases, whereas for temperatures outside of this range, bottle-brush polymers maintain a highly cylindrical symmetry in all configurational states.

    AB - Conformations of a single-component bottle-brush polymer with a fully flexible backbone under poor solvent conditions are studied by molecular dynamics simulations, using a coarse-grained bead–spring model with side chains of up to N = 40 effective monomers. By variation of the solvent quality and the grafting density σ with which side chains are grafted onto the flexible backbone, we study for backbone lengths of up to Nb = 100 the crossover from the brush/coil regime to the dense collapsed state. At lower temperatures, where collapsed chains with a constant monomer density are observed, the choice of the above parameters does not play any role and it is the total number of monomers that defines the dimensions of the chains. Furthermore, bottle-brush polymers with longer side chains possess higher spherical symmetry compared to polymers with lower side-chain lengths in contrast to what one may intuitively expect, as the stretching of the side chains is less important than the increase of their length. At higher temperatures, always below the Theta (Θ) temperature, coil-like configurations, similar to a single polymer chain, or brush-like configurations, similar to a homogeneous cylindrical bottle-brush polymer with a rigid backbone, are observed, depending on the choice of the particular parameters N and σ. In the crossover regime between the collapsed state (globule) and the coil/brush regime the acylindricity increases, whereas for temperatures outside of this range, bottle-brush polymers maintain a highly cylindrical symmetry in all configurational states.

    KW - soft matter

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    KW - condensed matter: structural

    KW - mechanical & thermal

    KW - chemical physics and physical chemistry

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