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

DMR 0805179：多膦酸盐及其与金属氧化物和多官能团阳离子的络合物技术摘要：众所周知，含有磷酸或磷酸基团的分子与包括金属、金属氧化物和阳离子在内的正电底物有很强的结合。因此，本项目的研究重点是获得1)膦酸酯共聚物的合成和性质的基础知识，以及2)这些聚合物与磁性纳米粒子和聚阳离子抗生素(氨基糖苷类)的络合物的性质。膦/双膦酸类官能团的特性可以通过提高其络合物的稳定性而使许多此类材料在生理介质中得到应用。我们的方法将是研究均多膦酸及其统计共聚物的合成和性质，如乙烯酰胺和乙酸乙烯酯(后水解为乙烯醇)等水溶性共聚单体，并探索可导致具有靶向MWs的功能低聚物的受控自由基聚合。定制的端基将与功能相容的聚醚嵌段反应，生成具有系统不同组成和相对分子质量的聚膦-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，以及具有强粘附性的改性聚醚低聚物。据我们所知，这是第一次研究具有不同结构的聚膦酸盐。在这些随机的、嵌段的和改性的聚合物结构中，膦/双膦酸基结构对金属氧化物纳米颗粒(即磁铁矿)和多阳离子(如氨基糖苷类)的络合作用的影响将被阐明。在DLVO理论和我们以前的工作的指导下，我们将测量和模拟水介质中络合物的结构，以将聚合物的相对分子质量和组成与络合物的溶液尺寸和性质联系起来。还预计，磁铁矿络合物与磷酸盐结合基团的稳定性将使受控簇合物能够组装，这将有助于理解如何在溶液中制备聚合物-金属氧化物组合体。非技术摘要：有压倒性的证据表明，磷酸和磷酸基团与无数底物强烈结合。重要的例子包括金属(用于提高耐腐蚀性)、金属氧化物纳米颗粒、牙釉质、羟基磷灰石(骨)和用于细胞内药物输送的阳离子抗生素。此外，许多基于与药物络合的聚合物的潜在药物释放系统在生物介质中被破坏，而磷-氧键的结合特性可以避免这一问题。因此，假设含有多个膦酸基的聚合物可以形成许多在生理条件下有效的生物材料络合物。本项目将研究含有磷-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。新的高分子材料的结构-性质关系可能导致抗生素的细胞内药物载体、用于癌症热疗的响应性磁性络合物、用于磁性细胞和蛋白质分离的改进材料、新的致动器材料、治疗骨骼疾病的新材料、新的牙科材料以及具有前所未有的生物成像能力的材料。该项目涉及广泛的跨学科，需要化学家、物理学家、工程师和微生物学家之间的合作。学生将在这种多学科的环境中接受教育，并将深入了解团队方法的重要性。他们将通过科学演示和中学项目向公众宣传，并通过在工业短期课程中教授实验室课程来接触工业劳动力。

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.