COLLABORATIVE RESEARCH: HYPERBRANCHED GLYCOPOLYMERS VIA CONTROLLED RADICAL POLYMERIZATIONS

在这个由化学部大分子、超分子和纳米化学项目资助的项目中，加州大学洛杉矶分校的Andrea Kasko和阿克伦大学的Coleen Pugh将开发合成方法来制备仿生糖基共聚物。 一系列糖基引发剂、单体和引发剂（引发剂/单体）将使用容易获得且廉价的起始材料和程序合成。 通过控制引发剂的自由基聚合，合成了一类新型超支化仿生糖（共）聚物，其中糖残基不仅可以侧挂在聚合物主链上，而且可以以其天然的环状形式存在于聚合物链中. 受控聚合将允许生产复杂结构，包括具有末端官能化的无规和嵌段共聚物。这些材料的分支结构将通过MS-MS、2-D NMR光谱和光散射分析来表征，并且聚合物的生物活性将通过评价生长因子的螯合和确定凝集素结合亲和力来表征。 更广泛的影响包括培训本科生和研究生，通过两所大学之间的合作加强研究和教育基础设施，通过科学奥林匹克聚合物探测活动以及通过互动网站和博客与高中化学课，以及这项研究对利用糖聚合物的科学和技术的潜在影响。这项工作解决了多糖化学合成中的一个长期问题（由糖单元组成的长链分子）：开发快速获得大量多糖并控制其组成和结构的方法。 这些类型的聚合物可以在生物医学中具有多种应用，并且可以用作治疗剂、药物载体、再生医学材料或诊断设备材料。

In this project funded by the Macromolecular, Supramolecular and Nanochemistry Program of the Chemistry Division, Andrea Kasko of the University of California at Los Angeles and Coleen Pugh of the University of Akron will develop synthetic methodologies to prepare biomimetic glycopolymers. A series of sugar-based initiators, monomers, and inimers (initiator/monomer)s will be synthesized using readily available and inexpensive starting materials and procedures. A new class of hyperbranched biomimetic glyco(co)polymers will be synthesized via controlled radical (co)polymerization of the inimers, in which the saccharide residues can be incorporated not only pendant to the polymer backbone, but also within the polymer chain in their native ring form. Controlled polymerizations will allow the production of complex structures, including random and block copolymers with end-functionalization. The branched structure of these materials will be characterized by MS-MS, 2-D NMR spectroscopy, and light scattering analysis, and the biological activity of the polymers will be characterized by evaluating the sequestration of growth factors and determining lectin binding affinity. The broader impacts involve training undergraduate and graduate students, enhancing research and education infrastructure through the collaboration between the two universities, participating in outreach to K-12 students via a Science Olympiad Polymer Detective activity and via an interactive website and blog with a high school chemistry class, and the potential impact of this research on science and technology that utilizes glycopolymers.This work addresses a longstanding issue in the chemical synthesis of polysaccharides (long chain molecules comprised of sugar units): developing methods to rapidly access large quantities of polysaccharides with control over their compositions and structures. These types of polymers could have multiple applications in biomedicine, and may find use as therapeutic agents, drug carriers, materials for regenerative medicine, or materials for diagnostic devices.