Cooperative Chiral Order in Polyisocyanates:  New Statistical Problems

Polyisocyanates with a random sequence of (R) and (S) pendant groups follow a chiral “majority rule”:  the optical activity of the polymers is dominated by whichever enantiomer is in the majority. In earlier work, this effect was explained theoretically through a mapping of the polymer system onto t...

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Bibliographic Details
Published in:Macromolecules 1998-04, Vol.31 (8), p.2488-2492
Main Authors: Selinger, J. V, Selinger, R. L. B
Format: Article
Language:English
Subjects:
Applied sciences
Electrical, magnetic and optical properties
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Properties and characterization
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Summary:Polyisocyanates with a random sequence of (R) and (S) pendant groups follow a chiral “majority rule”:  the optical activity of the polymers is dominated by whichever enantiomer is in the majority. In earlier work, this effect was explained theoretically through a mapping of the polymer system onto the random-field Ising model. Here, the theory is extended to a wider class of heteropolymers. The theory predicts that the introduction of achiral pendant groups into the random sequence should have remarkably little effect on the sharpness of the majority-rule curve. It further predicts that correlations in the handedness of neighboring pendant groups should reduce the sharpness of the majority-rule effect, while anticorrelations should enhance the sharpness of this effect.
ISSN:0024-9297
1520-5835
DOI:10.1021/ma971783k