Two Dimensional Polymerizations in Supramolecular Assemblies

超分子组装中的二维聚合

基本信息

批准号：
9619887
负责人：
Neal Armstrong
金额：
$ 28.5万
依托单位：
University of Arizona
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
1997
资助国家：
美国
起止时间：
1997-08-01 至 2001-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=9619887&HistoricalAwards=false
关键词：
Two Dimensional Polymerizations Supramolecular Assemblies

项目摘要

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. ***

9619887 O'Brien近年来引入了几种聚合超分子组件的方法。这些新的且不断发展的化学家具为生物学和材料科学具有特殊特性准备新的生物分子材料。新材料的设计和可再现制备的成功需要清楚地了解用于修改组件的聚合过程。 %% %%该提案的目的是提高我们对有组织培养基中聚合的理解，以允许利用新兴信息来控制聚合超分子材料的性质并准备新的大分子结构。双层的新兴图片相辅相成，对双层中的线性聚合的相当发达的理解相辅相成。组装中单体脂质的聚合以线性或交联的方式进行，具体取决于每个单体脂质的可聚合基团的数量。在任何一个疏水尾部中包含一个反应性部分的脂质或与亲水头组产生线性聚合物的脂质。脂质与每个疏水性尾部中反应性基团的聚合产生交联聚合物。相比之下，在相同的疏水尾部中具有不同反应性基团（双功能两亲物）的脂质的聚合不一定会产生交联的聚合物，因为如果这些组不足以分离，则聚合路径的相关性不足，可能会产生梯子聚合物而不是交联聚合物。首选的反应路径将取决于几个因素，包括间隔组的性质，分子组装中构象和扩散自由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的媒体首选的P Olymerization过程的影响，这项研究将依次与新设计的双功能两亲属家族一起检查。这些研究的发现将用于选择双功能单体，以制备由不同的聚合物组成的梯子样共聚物，例如聚（二烯）和聚（丙烯酸酯）。目的是利用我们对有组织培养基中聚合过程的理解来创建新型的可溶性共聚物，这些共聚物不容易通过溶液聚合来获得。此外，这些聚合研究将有助于设计双功能脂肪酸，以使单层或多层的交联聚合以不修改两亲属的亲水性头部组的方式。最后，该研究将利用对有组织组件中的交联过程的理解，以准备新的邻苯烷氨酸，以稳定局部性液体晶体。 ***