Two Dimensional Polymerizations in Supramolecular Assemblies

9619887奥布莱恩近年来介绍了几种制备超分子组装体的方法。 这些新的和不断发展的化学物质为制备具有生物科学和材料科学感兴趣的特定特性的新型生物分子材料提供了机会。 新材料的设计和可重复制备的成功需要对用于修改组件的聚合过程有清楚的了解。 本提案的目的是推进我们的理解聚合在有组织的媒体的方式，允许利用新兴的信息来控制聚合的超分子材料的性能，并准备新的大分子结构。 双层中线性聚合的合理发展的理解是由双层中交联聚合的新兴图片补充。 组装体中单体脂质的聚合以线性或交联方式进行，这取决于每个单体脂质的可聚合基团的数目。 在疏水性尾部或与亲水性头部基团缔合的任一个中含有单个反应性部分的脂质产生线性聚合物。 在每个疏水尾部中具有反应性基团的脂质的聚合产生交联聚合物。 相反，在相同疏水尾部具有不同反应性基团（双官能两亲物）的脂质的聚合不一定产生交联聚合物，因为如果基团不充分分离，聚合路径的相关性可能产生梯形聚合物而不是交联聚合物。 优选的反应路径将取决于几个因素，包括间隔基团的性质、分子组件内的构象和扩散自由度的程度以及可聚合基团的反应性。 为了更清楚地了解这些因素对有组织介质中优选聚合过程的影响，本研究将依次用一系列新设计的双官能两亲物进行研究。 从这些研究的结果将被用来选择双官能单体的制备梯形共聚物组成的不同的聚合物，例如聚（二烯）和聚（丙烯酸酯）。 我们的目标是利用我们对有组织介质中聚合过程的理解来产生通过溶液聚合不容易获得的新型可溶性共聚物。 此外，这些聚合研究将有助于设计用于单层或多层交联聚合的双官能脂肪酸，其方式不会改变两亲物的亲水性头基。 最后，本研究将利用对有序组装体中交联过程的理解来制备新型酞菁，用于稳定分散液晶。 ***

9619887 O'Brien Several methods to polymerize supramolecular assemblies have been introduced in recent years. These new and evolving chemistries open opportunities to prepare novel biomolecular materials with particular properties of interest to both biological and material sciences. Success in the design and reproducible preparation of new materials requires a clear understanding of the polymerization processes used to modify the assemblies. %%% The objective of this proposal is to advance our understanding of polymerizations in organized media in a manner that permits the utilization of the emerging information to control the properties of polymerized supramolecular materials and to prepare novel macromolecular architectures. The reasonably well-developed understanding of linear polymerizations in bilayers is complemented by the emerging picture of crosslinking polymerizations in bilayers. Polymerization of monomeric lipids in an assembly proceeds in a linear or crosslinking manner depending on the number of polymerizable groups per monomeric lipid. Lipids that contain a single reactive moiety in either of the hydrophobic tails or associated with the hydrophilic head group yield linear polymers. Polymerization of lipids with reactive groups in each hydrophobic tail yields crosslinked polymers. In contrast the polymerization of lipids that have different reactive groups (bifunctional amphiphiles) in the same hydrophobic tail does not necessarily yield crosslinked polymers, because if the groups are insufficiently separated the correlation of the polymerization paths could produce ladder polymers rather than crosslinked polymers. The preferred reaction path will depend on several factors including the nature of the spacer group, the extent of conformational and diffusional freedom within the molecular assembly, and the reactivity of the polymerizable groups. In order to obtain a clearer understanding of the effect of these factors on the preferred p olymerization process in organized media this research will examine each in turn with a family of newly designed bifunctional amphiphiles. The findings from these studies will be used to select bifunctional monomers for the preparation of ladder-like copolymers composed of dissimilar polymers, e.g. poly(diene) and poly(acrylate). The objective is to utilize our understanding of the polymerization process in organized media to create novel soluble copolymers that are not readily available through solution polymerizations. In addition these polymerization studies will aid in the design of bifunctional fatty acids for the crosslinking polymerization of monolayers or multilayers in a manner that does not modify the hydrophilic head group of the amphiphile. Finally the research will utilize the understanding of crosslinking processes in organized assemblies to prepare novel phthalocyanines for the stabilization of discotic liquid crystals. ***