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.
Cooperative phenomena, described by one-dimensional statistical physical methods, are observed between the enantiomeric characteristics of monomeric materials and the polymers they produce. The effect of minute energies associated with this amplified chirality, although currently not interpretable, can be easily measured. Nonlinear relationships between enantiomeric excess or enantiomeric content and polymer properties may offer the possibility of developing chiral catalysts and chiral chromatographic materials in which the burden of large enantiomeric excess or content may be considerably alleviated. New approaches to information and sensor technology may become possible.
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