Unusual Stereochemical Opportunities in Extended Helical Conformations

这项来自化学学部有机动力学项目和材料研究部聚合物项目的资助支持了格林教授和莱文博士在理工大学的持续工作。本研究结果将对聚合物的左旋或右旋性质有新的认识和认识。本文还将探讨控制右旋或左旋螺旋优先形成的因素。由于生物聚合物，如肽和DNA，可以存在于右手或左手螺旋，这项工作是特别感兴趣的。Drs。Green和Levon将在三个领域提供新的和重要的信息，这些信息都与单体的手性如何影响聚合物的螺旋手性有关。首先，研究手性中心对异氰酸酯聚合物手性螺旋度的影响。研究发现，R-1-氘-己基异氰酸酯中氘取代的手性中心对多异氰酸酯的螺旋手性有深远的影响。这一观察结果将被进一步研究，以及由r -2-二氘己基异氰酸酯产生的聚合物的螺旋手性。在第二方面，将研究n -羧基氢化物单体中含有联苯的侧链的螺旋扭与聚谷氨酸聚合物螺旋度之间的关系。在第三个领域，将研究多异氰酸酯凝胶化作为单体立体化学的功能。

This grant from the Organic Dynamics Program of the Chemistry Division and the Polymers Program of the Division of Materials Research supports the continuing work of Professor Green and Dr. Levon at the Polytechnic University. The results of this research will give new understanding and insight to the right or left hand helical nature of polymers. The factors that control the preferential formation of right- or left- handed helices will be explored. Since bio-polymers, such as peptides and DNA, can exist in right- or left- handed helices, this work is of particular interest. Drs. Green and Levon will provide new and important information in three areas, of which all are related to how the chirality of the monomers effect the helical chirality of the polymers. In the first area, the effect of a chiral center on the chiral helicity of isocyanate polymers will be studied. It has been found that a chiral center by virtue of deuterium substitution in R-1- deuteriohexylisocyanate had a profound effect on the helical chirality of the polyisocyanate. This observation will be studied further as well as the helical chirality of the polymer resulting from R-2-deuteriohexylisocyanate. In the second area, a study will be made of the relationship between helical twist of a side chain containing a biphenyl group in an N-carboxyanhydride monomer and helicity of the polyglutamate polymer. In the third area, the gelation of polyisocyanides as function of the stereochemistry of the monomer will be investigated.