Dynamic-covalent Interactions for Enhanced Stabilization of Kinetically-arrested Nanoparticles

动态共价相互作用增强动力学捕获纳米颗粒的稳定性

• 批准号: 2003789
• 负责人: Margarita Herrera-Alonso
• 金额: $ 45万
• 依托单位: Colorado State University
• 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: 2020-07-01 至 2024-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2003789&HistoricalAwards=false
• 关键词: Dynamic; covalent; Interactions; Enhanced; Stabilization

In this project funded by the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Professor Margarita Herrera-Alonso at Colorado State University is using dynamic-covalent interactions to enhance the stability of nanoparticles generated from solution in the self-assembly of polymers. Dynamic-covalent interactions refer to reversible chemical bond forming/breaking during a chemical reaction. It offers “error-correction” of the targeted chemical structures because the reactants are chosen in such a way that chemical bonds during the reaction form in a predictable, precise and controlled manner. This synthetic strategy allows for the preparation of very complex molecules from discrete molecular building blocks. Applications of this chemistry are found in numerous areas of biotechnology and medicine. Of particular interest is the design of artificial polymers for targeted delivery of drugs in a human body. In this research, large molecules with complex architectures are prepared that have water-loving and water-hating segments. These polymers also contain the chemical element boron that triggers dynamic-covalent chemistry during self-assembly in solution. Educational impacts of this work are focused on the incorporation of research results into graduate and undergraduate courses and training of students at graduate and undergraduate levels. Efforts to retain undergraduate underrepresented minorities are undertaken through mentoring of student members of the Hispanic Association of Colleges and Universities. Outreach activities center on recruiting activities and summer research opportunities for undergraduates through The Colorado-Wyoming Alliance for Minority Participation (CO-WY AMP). This research centers around the study of dynamic-covalent interactions to enhance the stability of kinetically-arrested nanoparticles generated by the solution self-assembly of amphiphilic bottlebrushes. The first objective of the project focuses on generating a library of block-like bottlebrush copolymers exhibiting functional moieties susceptible to dynamic-covalent (DC) interactions. Inspired by the role of boron as a stabilizer in nature, the chemistry utilizes boronic acid-diol interactions for shell stabilization. Complementary macromolecular crosslinkers are also prepared. In the second objective, the kinetic features of self-assembly from block-like bottlebrushes are examined in order to obtain insight regarding their assembly mechanism, effect of processing conditions on nanoparticle properties, and characteristic aggregation times. The encapsulation of a family of solutes mediated by block-like bottlebrushes to understand fundamental differences of the process and the resulting constructs with respect to systems based on linear amphiphiles of similar chemical composition is additionally investigated. Lastly, nanoparticle stabilization through shell-crosslinking via boronate ester formation between block-like bottlebrushes and either small-molecule or macromolecular crosslinkers is systematically evaluated. The reversible nature of these interactions is harnessed to allow for controlled spatio/temporal release under specific environmental triggers, including low pH, oxidative environments and in the presence of competing cis-diols. The overall goal is to achieve a better understanding of the effects of macromolecular architecture on kinetically-arrested self-assemblies, and the uniqueness of bottlebrush-based constructs with respect to their linear analogs. This research could provide fundamental and technological insights regarding the dynamics of bottlebrush self-assembly and stabilization strategies based on a thermodynamically-driven dynamic-covalent interaction between boronic acids and cis-diol containing compounds.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.

在该项目由大分子，超分子和纳米化学计划资助的项目中，科罗拉多州立大学的玛格丽塔·埃雷拉·阿隆索（Margarita Herrera-Alonso）教授使用动态交易互动来增强Polymers自组装溶液中产生的纳米颗粒的稳定性。动态共价相互作用是指化学反应过程中可逆的化学键形成/破裂。它提供靶向化学结构的“误差”，因为选择反应物以可预测，精确和受控方式的反应形式的化学键在反应形式中。这种合成策略允许从离散分子构建块制备非常复杂的分子。在生物技术和医学的许多领域都发现了这种化学的应用。特别令人感兴趣的是人工聚合物的设计，用于靶向人体中的药物。在这项研究中，制备具有复杂体系结构的大分子，这些分子具有热爱水和讨厌水的段。这些聚合物还含有化学元件硼，该硼在溶液中自组装过程中触发动态共价化学。这项工作的教育影响着重于将研究结果纳入研究生和本科课程，并在研究生和本科阶段对学生进行培训。通过对西班牙裔学院和大学协会的学生进行心理化，为保留本科生不足的少数群体而努力做出了努力。外展活动中心通过少数群体参与的招聘活动和夏季研究机会，为本科生提供本科生（Co-Wy Amp）。这项研究围绕研究动态共价相互作用的研究，以增强由两亲奶瓶刷的溶液自组装产生的动力学安装纳米颗粒的稳定性。该项目的第一个目标是生成一个类似块状瓶装共聚物的库，激发了受动态共价（DC）相互作用的功能部分。受到硼在本质上稳定剂的作用的启发，化学利用硼酸二醇相互作用来稳定壳。还准备了互补的大分子交联。在第二个目标中，检查了从块状瓶手术中进行自组装的动力学特征，以获取有关其组装机制，加工条件对纳米颗粒性质的影响以及特征聚集时间的见解。另外研究了由块状瓶洗手剂介导的一系列太阳系，以了解该过程的基本差异以及基于类似化学成分的线性两亲物的系统的基本差异。最后，系统地评估了纳米颗粒通过钢酸酯形成的岩石酯形成和小分子或大分子或大分子交叉链接器之间的岩石固定。这些相互作用的可逆性是可以利用的，以便在特定的环境触发器（包括低pH，氧化环境以及存在​​竞争的顺式二醇）下进行控制的空间/时间释放。总体目标是更好地理解大分子结构对动力学自由组件的影响，以及基于瓶装的构造的独特性，相对于它们的线性类似物。这项研究可以提供有关基于热力学驱动的动态与硼酸和含有化合物的顺式二醇的动态和稳定策略动态和稳定策略动态的基本和技术见解。这奖反映了NSF的稳定任务，并通过评估了基础的智力效果，并通过评估了基础的范围和广泛的影响。