Thermodynamics and Chain Dynamics in Spin-labeled Peptide Block Copolymer Assemblies

自旋标记肽嵌段共聚物组装体中的热力学和链动力学

• 批准号: 2003366
• 负责人: Gail Fanucci
• 金额: $ 60万
• 依托单位: University of Florida
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-06-01 至 2025-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2003366&HistoricalAwards=false
• 关键词: Thermodynamics; Chain; Dynamics; Spin; labeled

With this award, the Macromolecular, Supramolecular, and Nanochemistry Program in the Division of Chemistry is funding Professors Daniel A. Savin and Gail E. Fanucci of the Department of Chemistry at University of Florida to explore the self-assembly of spin-labeled, peptide containing block polymers to discover how molecular level structure and interactions can result in global morphology changes. Given the wealth of knowledge that peptide chemists have regarding protein structure, folding, and function, polymer scientists can use this toolbox and apply the same principles to synthetic polymer-polypeptide hybrid systems. From an application standpoint, peptide-based hybrid materials have shown potential as pH sensitive drug delivery vehicles and hydrogels that have advantages in terms ofbiocompatibility. Responsive materials have also been used to produce molecular actuators and switchable surfaces. The training program in the Savin and Fanucci groups integrates teaching and research in a broad range of disciplines including chemistry, physics, biochemistry and polymer science, from K-12 to postdoctoral researchers. Students gain a comprehensive understanding of polymers andbiomaterials in many areas of synthesis, characterization, morphology, spectroscopy, scattering and rheology. This multidisciplinary approach is essential not only from an educational standpoint, but also to produce well-rounded graduates who are attractive to a variety of employers in both academic and industrial settings. The team is committed to broadening participation and strongly encourages research participation by undergraduates. The outreach program continues two highly successful programs by Savin and Fanucci at the K-5 and 9-12 levels, respectively, and adds a new program aimed at mentoring local foster children at the high school level. This research is focused on utilizing site specific spin-labels as probes to characterize the local environment and monitor changes in the self-assembly and morphological transitions in peptide-based block copolymer assemblies. Macroinitiators are prepared that contain the radical spin label agent TEMPO, and aminoethylpiperazine. Copolymers are then synthesized by ring opening of N-carboxyanhydrides of amino acids. Spectroscopic tools such as electron paramagnetic resonance and Overhauser dynamic nuclear polarization NMR spectroscopy are used to provide local interrogation of end-to-end distributions, hydration, accessibility, and segmental dynamics in responsive block copolymer assemblies. This characterization is coupled with morphology characterization where light scattering and electron microscopy are used to determine critical parameters such as size, shape, aggregation number, and the average chain density at the interface of the assemblies. Results associated with this research could enable the establishment of a new analytical platform to determine local conformational, thermodynamic, and dynamic properties of polymers in assemblies.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

有了这个奖项，化学系的大分子、超分子和纳米化学项目资助了丹尼尔教授。Savin和Gail E. Fanucci博士在佛罗里达大学的化学系，探索自旋标记的，含有嵌段聚合物的肽的自组装，以发现分子水平的结构和相互作用如何导致全局形态的变化。鉴于肽化学家对蛋白质结构、折叠和功能的丰富知识，聚合物科学家可以使用这个工具箱，将相同的原理应用于合成聚合物-多肽杂交系统。从应用的角度来看，基于肽的杂化材料已显示出作为pH敏感的药物递送载体和水凝胶的潜力，其在生物相容性方面具有优势。响应材料也已用于生产分子致动器和可切换表面。Savin和Fanucci集团的培训计划整合了广泛学科的教学和研究，包括化学，物理，生物化学和聚合物科学，从K-12到博士后研究人员。学生将在合成、表征、形态学、光谱学、散射和流变学等多个领域全面了解聚合物和生物材料。这种多学科的方法是必不可少的，不仅从教育的角度来看，但也产生全面的毕业生谁是有吸引力的各种雇主在学术和工业环境。该团队致力于扩大参与，并强烈鼓励本科生参与研究。该推广计划延续了Savin和Fanucci分别在K-5和9-12级别的两个非常成功的计划，并增加了一个旨在指导当地高中寄养儿童的新计划。本研究的重点是利用位点特异性自旋标记作为探针来表征局部环境，并监测基于肽的嵌段共聚物组装体中自组装和形态转变的变化。制备含有自由基自旋标记剂克里思和氨基乙基哌嗪的大分子引发剂。然后通过氨基酸的N-羧基酸酐的开环合成共聚物。光谱工具，如电子顺磁共振和Overhauser动态核极化NMR光谱，用于提供本地询问的端到端的分布，水合作用，可访问性，和响应嵌段共聚物组件中的链段动力学。该表征与形态表征相结合，其中使用光散射和电子显微镜来确定关键参数，如尺寸、形状、聚集数和组装体界面处的平均链密度。与这项研究相关的结果可以建立一个新的分析平台，以确定聚合物在assemblies.This奖项的法定使命的局部构象，热力学和动力学性质，并已被认为是值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估的支持。