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Science 30 June 1995:
Vol. 268. no. 5219, pp. 1860 - 1866
DOI: 10.1126/science.268.5219.1860
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Articles

A Helical Polymer with a Cooperative Response to Chiral Information

Mark M. Green 1, Norman C. Peterson 1, Takahiro Sato 2, Akio Teramoto 2, Robert Cook 3, and Shneior Lifson 4

1 Department of Chemistry and the Herman F. Mark Polymer Research Institute, Polytechnic University, Six Metrotech Center, Brooklyn, NY 11201, USA.
2 Department of Macromolecular Science, Faculty of Science, Osaka University, Toyonaka, Osaka 560, Japan
3 Lawrence Livermore National Laboratory, Livermore, CA 94550, USA.
4 Department of Chemical Physics, Weizmann Institute of Science, Rehovot, 76100, Israel

Polyisocyanates, long studied as theoretical models for wormlike chains in dilute solution and liquid crystals, differ from their biological helical analogs in the absence of a pre-determined helical sense. These polymers have an unusual sensitivity to chiral effects that arises from a structure in which alternating right- and left-handed long helical blocks are separated by infrequent and mobile helical reversals. Statistical thermodynamic methods yield an exact description of the polymer and the cooperative nature of its chiral properties. Minute energies that favor one of the helical senses drive easily measurable conformational changes, even though such energies may be extremely difficult to calculate from structural theory. In addition, the chiral nature of the polymer can be used to test theoretical ideas concerned with cholesteric liquid crystals, one of which solves the problem of assigning the helical sense.


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