Polyphosphonates and their Complexes with Metal Oxides and Multi-Functional Cations

DMR 0805179：聚膦酸酯及其与金属氧化物和多官能阳离子的络合物技术概述：众所周知，含有膦酸或磷酸根基团的分子与包括金属和金属氧化物和阳离子的正电性底物强烈结合。 因此，本项目的研究重点旨在获得以下基础知识：1）膦酸酯共聚物的合成和性质，以及2）这些聚合物与磁铁矿纳米颗粒和聚阳离子抗生素（氨基糖苷类）的复合物的性质。 膦酸酯/双膦酸酯官能团的特性可以通过增强它们的复合物的稳定性而使许多这样的材料能够在生理介质中使用。 我们的方法将是研究均聚膦酸及其与水溶性共聚单体如乙烯酰胺和乙酸乙烯酯（后水解为乙烯醇）的统计共聚物的合成和性质，并探索可控的自由基聚合，这可能导致具有目标分子量的功能性低聚物。 定制的端基将与功能相容的聚醚嵌段反应，以产生具有系统变化的组成和分子量的聚膦酸酯-非离子嵌段共聚物。 这项研究将导致新的统计和嵌段共聚物，以及改性聚醚低聚物具有强粘合性能。 据我们所知，这是第一次研究不同结构的聚膦酸酯。 这些无规、嵌段和改性聚合物结构中的膦酸酯/双膦酸酯部分对与金属氧化物纳米颗粒络合的影响（即，磁铁矿）和聚阳离子如氨基糖苷类。在水介质中的复合物的结构将被测量和建模，DLVO理论和我们以前的工作的指导下，涉及聚合物分子量和组合物的解决方案的大小和性质的复合物。还可以预期，磁铁矿配合物与膦酸酯结合基团的稳定性将使控制集群的组装，这将有助于理解如何制备聚合物-金属氧化物组件在solution.Non-Technical摘要：有压倒性的证据表明，膦酸和磷酸基团强烈结合到无数的基板。重要的例子包括金属（赋予耐腐蚀性）、金属氧化物纳米颗粒、牙釉质、羟基磷灰石（骨）和用于细胞内药物递送的阳离子抗生素。 此外，许多潜在的药物传递系统的基础上与药物复合的聚合物在生物介质中被破坏，磷-氧键的结合特性可以避免这个问题。 因此，假设含有多个膦酸酯基团的聚合物可以使许多生物材料复合物能够在生理条件下有效。 该项目将研究含有磷-氧键的新型聚合物的合成和性质，以及将这些聚合物与磁性纳米颗粒和关键抗生素络合的方法。 新型高分子材料的结构-性能关系可能导致用于抗生素的细胞内药物载体、用于癌症热疗的响应性磁性复合物、用于磁性细胞和蛋白质分离的改进材料、新型致动器材料、用于治疗骨病的新材料、新型牙科材料以及具有前所未有的生物成像能力的材料。该项目是广泛的跨学科，需要化学家，物理学家，工程师和微生物学家之间的合作。 学生将在这个多学科的环境中接受教育，并将深入了解团队合作的重要性。 他们将通过科学演示和中学课程向公众推广，并通过在工业短期课程中教授实验室课程向工业劳动力推广。

DMR 0805179: Polyphosphonates and their Complexes with Metal Oxides and Multifunctional CationsTECHNICAL SUMMARY: Molecules containing phosphonic acid or phosphate groups are well-known to bind strongly with electropositive substrates including metals and metal oxides and cations. Thus, research thrusts in this project are aimed toward gaining fundamental knowledge of 1) synthesis and properties of phosphonate copolymers, and 2) properties of complexes of those polymers with magnetite nanoparticles and polycationic antibiotics (aminoglycosides). The characteristics of the phosphonate/bisphosphonate functional groups could enable the use of many such materials in physiological media by enhancing stabilities of their complexes. Our approach will be to investigate the synthesis and properties of homopolyphosphonic acids and their statistical copolymers with water-soluble comonomers such as vinylamides and vinyl acetate (post-hydrolyzed to vinyl alcohol), and to explore controlled radical polymerizations that could lead to functional oligomers with targeted MWs. Tailored endgroups will be reacted with functionally-compatible polyether blocks to produce polyphosphonate-nonionic block copolymers with systematically varied compositions and MWs. This research will lead to new statistical and block copolymers, as well as modified polyether oligomers with strongly-adhesive properties. To our knowledge, this is the first study of polyphosphonates with different architectures. Effects of phosphonate/bisphosphonate moieties in these random, block and modified-polymer architectures on complexation with metal oxide nanoparticles (i.e., magnetite) and polycations such as the aminoglycosides will be elucidated. Structures of the complexes in aqueous media will be measured and modeled, guided by DLVO theory and our previous work, to relate polymer MW and composition to the solution sizes and properties of the complexes. It is also anticipated that the stability of magnetite complexes with the phosphonate binding groups will enable assembly of controlled clusters, and this will contribute to an understanding of how to prepare polymer-metal oxide assemblies in solution.NON-TECHNICAL SUMMARY:There is overwhelming evidence that phosphonic acid and phosphate groups bind strongly to a myriad of substrates. Important examples include metals (to impart corrosion resistance), metal oxide nanoparticles, tooth enamel, hydroxyapetite (bone) and cationic antibiotics for intracellular drug delivery. Moreover, many potential drug delivery systems based on polymers complexed with drugs are destroyed in biological media and the binding characteristics of phosphorus-oxygen bonds may avoid this problem. Thus, it is hypothesized that polymers containing multiple phosphonate groups could enable many biomaterial complexes that could be effective in physiological conditions. This project will investigate the synthesis and properties of new polymers containing phosphorus-oxygen bonds and methods for complexing these polymers to magnetic nanoparticles and key antibiotics. Structure-property relationships of the new macromolecular materials could lead to intracellular drug carriers for antibiotics, responsive magnetic complexes for hyperthermia treatments for cancer, improved materials for magnetic cell and protein separations, new actuator materials, new materials for treating bone diseases, new dental materials, and materials with unprecedented biological imaging capabilities. The project is broadly interdisciplinary, and requires collaboration among chemists, physicists, engineers and microbiologists. Students will be educated in this multi-disciplinary environment, and will gain insight into the importance of a teamed approach. They will outreach to the public through science demonstrations and middle school programs, and to the industrial workforce by teaching laboratory sessions in industrial short courses.