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Polymer Classification: Crystallinity01:21

Polymer Classification: Crystallinity

Unlike ionic or small covalent molecules, polymers do not form crystalline solids due to the diffusion limitations of their long-chain structures. However, polymers contain microscopic crystalline domains separated by amorphous domains.
Crystalline domains are the regions where polymer chains are aligned in an orderly manner and held together in proximity by intermolecular forces. For example, chains in the crystalline domains of polyethylene and nylon are bound together by van der Waals...

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Related Experiment Video

Updated: Jul 27, 2026

Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
16:24

Controlling the Size, Shape and Stability of Supramolecular Polymers in Water

Published on: August 2, 2012

Controlling molecular crystal polymorphism with self-assembled monolayer templates.

Rupa Hiremath1, Joseph A Basile, Stephen W Varney

  • 1Department of Chemistry, Georgetown University, 37th and "O" Streets NW, Washington, DC 20057-1227, USA.

Journal of the American Chemical Society
|December 22, 2005
PubMed
Summary

Controlling crystal polymorphism in 1,3-bis(m-nitrophenyl) urea (MNPU) is achieved using gold-thiol self-assembled monolayers (SAMs). These SAMs selectively template the nucleation and growth of specific MNPU crystalline phases, ensuring high purity.

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Area of Science:

  • Solid-state chemistry
  • Materials science
  • Crystallization science

Background:

  • Crystal polymorphism presents challenges in solid-state chemistry with significant commercial implications.
  • 1,3-bis(m-nitrophenyl) urea (MNPU) is a molecular crystal system known to exhibit multiple crystalline forms.
  • Controlling the formation of specific polymorphs is crucial for material properties and applications.

Purpose of the Study:

  • To investigate the use of gold-thiol self-assembled monolayers (SAMs) for selective templating of MNPU polymorphs.
  • To demonstrate the ability of SAMs to control nucleation and growth of specific crystalline phases.
  • To understand the interfacial interactions governing polymorph selectivity.

Main Methods:

  • Synthesis of substituted 4'-X-mercaptobiphenyls (X = H, I, Br) for gold-thiol SAMs.
  • Crystallization of MNPU in the presence of functionalized SAM surfaces.
  • Characterization of MNPU polymorphs formed under SAM influence.
  • Analysis of SAM/crystal interfaces for interaction studies.

Main Results:

  • Gold-thiol SAMs effectively templated the selective nucleation and growth of alpha-, beta-, and gamma-MNPU phases.
  • Polymorph control was achieved under diverse solution conditions, yielding high phase purity.
  • Specific SAM compositions correlated with the selective formation of distinct MNPU polymorphs.

Conclusions:

  • Self-assembled monolayers provide a robust strategy for controlling crystal polymorphism in MNPU.
  • The observed selectivity arises from a combination of 2D lattice matching and local chemical interactions at the interface.
  • This approach offers a pathway to engineer crystalline materials with desired polymorphs for various applications.