Organic nanoparticles with tunable size and rigidity by hyperbranching and cross- linking using microemulsion ATRP

• 成果类型: Article
• 署名作者: Yin, Rongguan; Tarnsangpradit, Jirameth; Gul, Akhtar; Jeong, Jaepil; Hu, Xiaolei; Zhao, Yuqi; Wu, Hanshu; Li, Qiqi; Fytas, George; Karim, Alamgir; Bockstaller, Michael R.; Matyjaszewski, Krzysztof
• 署名单位: Carnegie Mellon University; Carnegie Mellon University; University of Houston System; University of Houston; Max Planck Society
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-9528
• DOI: 10.1073/pnas.2406337121
• 发表日期: 2024-07-16
• 关键词: transfer radical polymerization; inorganic nanoparticles; silica nanoparticles; graft modification; miniemulsion atrp; particle brushes; nanocomposites; surface; arget; polystyrene

摘要

Unlike inorganic nanoparticles, organic nanoparticles (oNPs) offer the advantage of interior tailorability, thereby enabling the controlled variation of physicochemical characteristics and functionalities, for example, by incorporation of diverse functional small molecules. In this study, a unique inimer-based microemulsion approach is presented to realize oNPs with enhanced control of chemical and mechanical properties by deliberate variation of the degree of hyperbranching or cross-linking. The use of anionic cosurfactants led to oNPs with superior uniformity. Benefitting from the high initiator concentration from inimer and preserved chain-end functionality during atom transfer radical polymerization (ATRP), the capability of oNPs as a multifunctional macroinitiator for the subsequent surface-initiated ATRP was demonstrated. This facilitated the synthesis of densely tethered poly(methyl methacrylate) brush oNPs. Detailed analysis revealed that exceptionally high grafting densities (similar to 1 nm(-2)) were attributable to multilayer surface grafting from oNPs due to the hyperbranched macromolecular architecture. The ability to control functional attributes along with elastic properties renders this bottom-up synthetic strategy of macroinitiator-type oNPs a unique platform for realizing functional materials with a broad spectrum of applications.