The macromolecular route to chiral amplification

Mark M. Green, Ji Woong Park, Takahiro Sato, Akio Teramoto, Shneior Lifson, Robin L B Selinger, Jonathan V. Selinger

Research output: Contribution to journalArticle

Abstract

Polymers show cooperative phenomena for almost all of their properties, and this is no less true for the optical activity of chiral polymers. This phenomena was first observed by the 'Italian School' in their early work following the discovery of stereoregular polymerization, and let to observations of nonlinear relationships between enantiomeric characteristics of monomeric materials used in polymerizations and the polymers produced. These observations confirmed the hypothesis that the conformations of these polymers in the melt and dissolved states resembled those found in the solid crystal. In recent years a version of the Nylons, which failed to make the grade as a fiber, turned out to carry these cooperative properties of chirality to an extreme. Minute chiral forces control the chain properties, allowing experiments in which chirality arising from isotopic substitution, or solvation effects, or even nearly racemic states can be studied. Statistical physics and the one-dimensional Ising model describe the properties of these polymers in quantitative perfection and yield insight into how to manipulate the chirality and the polymer properties to gain even higher amplification of the chiral forces. Through work on such disparate materials as vinyl polymers and polyisocyanates, we discover the structural boundaries for these observations and therefore which other polymeric and supramolecular systems may behave similarly. This is already being seen. However, these studies also demonstrate that structural theory appears inadequate to interpret the small energies driving these chiral effects, and this has parallels in other areas where equilibrium states are balanced on cooperatively driven forces.

Original languageEnglish (US)
Pages (from-to)3139-3154
Number of pages16
JournalAngewandte Chemie - International Edition
Volume38
Issue number21
StatePublished - Nov 2 1999

Fingerprint

Amplification
Polymers
Chirality
Polymerization
Ising model
Polyurethanes
Nylons
Solvation
Force control
Conformations
Substitution reactions
Physics
Crystals
Fibers
Experiments

Keywords

  • Asymmetric amplification
  • Chirality
  • Helical structures
  • Polymers

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Green, M. M., Park, J. W., Sato, T., Teramoto, A., Lifson, S., Selinger, R. L. B., & Selinger, J. V. (1999). The macromolecular route to chiral amplification. Angewandte Chemie - International Edition, 38(21), 3139-3154.

The macromolecular route to chiral amplification. / Green, Mark M.; Park, Ji Woong; Sato, Takahiro; Teramoto, Akio; Lifson, Shneior; Selinger, Robin L B; Selinger, Jonathan V.

In: Angewandte Chemie - International Edition, Vol. 38, No. 21, 02.11.1999, p. 3139-3154.

Research output: Contribution to journalArticle

Green, MM, Park, JW, Sato, T, Teramoto, A, Lifson, S, Selinger, RLB & Selinger, JV 1999, 'The macromolecular route to chiral amplification', Angewandte Chemie - International Edition, vol. 38, no. 21, pp. 3139-3154.
Green MM, Park JW, Sato T, Teramoto A, Lifson S, Selinger RLB et al. The macromolecular route to chiral amplification. Angewandte Chemie - International Edition. 1999 Nov 2;38(21):3139-3154.
Green, Mark M. ; Park, Ji Woong ; Sato, Takahiro ; Teramoto, Akio ; Lifson, Shneior ; Selinger, Robin L B ; Selinger, Jonathan V. / The macromolecular route to chiral amplification. In: Angewandte Chemie - International Edition. 1999 ; Vol. 38, No. 21. pp. 3139-3154.
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