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Chain molecules at high densities at interfaces.

K A Dill1, J Naghizadeh, J A Marqusee

  • 1Department of Pharmaceutical Chemistry, University of California, San Francisco 94143.

Annual Review of Physical Chemistry
|January 1, 1988
PubMed
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Highly concentrated polymers near interfaces experience constraints from boundaries, neighboring chains, and chain length. These factors influence polymer configuration and properties, differing from bulk behavior.

Area of Science:

  • Polymer Physics
  • Materials Science
  • Physical Chemistry

Background:

  • Polymers at interfaces exhibit unique behavior compared to bulk materials.
  • Understanding these interfacial effects is crucial for various applications.

Purpose of the Study:

  • To review the fundamental principles governing polymer chain behavior at sharp interfaces.
  • To elucidate the constraints affecting highly concentrated polymers near boundaries.

Main Methods:

  • Theoretical review of interfacial constraints on polymer chains.
  • Analysis of entropy maximization and configurational disorder.
  • Comparison of theoretical predictions with experimental observations.

Main Results:

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  • Identified three key constraints: boundary exclusion, inter-chain interactions, and chain length-dependent effects (symmetry vs. fixed length).
  • Demonstrated that polymers at equilibrium maximize entropy, leading to increased configurational disorder.
  • Observed that interfacial effects on polymer conformation are typically localized (5-10 Å) but can influence properties over longer distances.

    • Conclusions:

    • The established theory accurately predicts conformational and mixing properties of polymers in diverse systems.
    • Applicability spans interfaces, semicrystalline polymers, alkane crystals, chromatography stationary phases, and amphiphilic aggregates (membranes, micelles).