Macromolecular-bottlebrush polymeric gels with tissue-mimetic swelling and mechanical properties

具有模拟组织膨胀和机械性能的高分子瓶刷聚合物凝胶

• 批准号: 2004048
• 负责人: Sergei Sheiko
• 金额: $ 60万
• 依托单位: University of North Carolina at Chapel Hill
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-05-01 至 2024-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2004048&HistoricalAwards=false
• 关键词: Macromolecular; bottlebrush; polymeric; gels; tissue

NON-TECHNICAL SUMMARYLiving tissues are distinct in their ability to seamlessly span a range of mechanical properties from ultra-soft brain to super-tough cartilage at nearly constant water fraction. On the contrary, synthetic analogs of tissues (i.e. polymeric gels) are currently not capable to control the amount of water without affecting their mechanics. A new class of polymeric materials based on bottlebrush-macromolecular architectures is proposed here to enable independent and programmable control over gel composition and mechanical properties. In contrast to traditional linear polymers, the bottlebrush architecture introduces a myriad of side chains or “bristles” that afford additional molecular parameters to tune softness without changing the water fraction. Furthermore, tailoring the chemistry of side-chain ends will empower novel applications such as programmable and injectable materials for additive manufacturing of tissue-mimetic devices. The proposed novel class of polymeric gels will provide ample opportunities for interdisciplinary research through integration of cutting-edge polymer chemistry, soft-matter physics, and emerging technologies that may lead to breakthroughs in many applications such as biomedical devices, tissue-engineering scaffolds, and soft robotics. TECHNICAL SUMMARYThe project will address three fundamental challenges. First, the equilibrium swelling ratio and gel’s mechanical properties will be separately correlated with architectural parameters of brush-like networks such as the side chain length and grafting density. Triangulation of architecture-swelling-mechanics correlations will afford independent control over swelling, softness, and non-linear mechanical response. For example, this will create an unprecedented series of synthetic gels with the same solvent fraction, but widely different moduli varying within several orders of magnitude. The second goal is to design brush-like mesoblocks that enable solvent-free injection of tissue-mimetic elastomers. The challenge is to control curing time from seconds to days separate from mechanical properties of fully cured polymer networks. Lastly, successful implementation of goals 1 and 2 will enable a new class of bioink materials based on thermosensitive hydrogels that can inject and 3D-print objects with well-defined solvent fractions and mechanical properties. The main challenge here is to integrate controlled-temperature gelation of printed materials with the design-by-architecture objectives pursued in goals 1 and 2.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.

非技术概要活体组织的独特之处在于，它们能够在几乎恒定的水含量下无缝地涵盖从超柔软的大脑到超坚韧的软骨的一系列机械特性。相反，目前还没有组织的合成类似物（即聚合物凝胶）。这里提出了一种基于瓶刷高分子结构的新型聚合物材料，能够控制水量而不影响其力学性能，以实现对凝胶成分和机械性能的独立和可编程控制。与传统的线性聚合物相比，洗瓶刷结构引入了无数的侧链或“刷毛”，可以提供额外的分子参数来调节柔软度，而无需改变水含量。此外，定制侧链末端的化学性质将赋予诸如此类的新颖应用。用于组织模拟装置增材制造的可编程和可注射材料，通过整合尖端聚合物化学、软物质物理学和可能导致的新兴技术，新型聚合物凝胶将为跨学科研究提供充足的机会。在生物医学设备、组织工程支架和软机器人等许多应用中取得突破 技术摘要 该项目将解决三个基本挑战，首先，溶胀平衡比和凝胶的机械性能将分别与刷状网络的结构参数相关。例如，侧链长度和接枝密度的结构-膨胀-力学相关性将提供对膨胀、柔软度和非线性机械响应的独立控制。第二个目标是设计刷状介观块，能够实现无溶剂注射组织模拟弹性体。挑战是将固化时间控制在几秒到几秒之间。最后，成功实现目标 1 和 2 将使基于热敏水凝胶的新型生物墨水材料能够使用明确的溶剂注射和 3D 打印物体。这里的主要挑战是将印刷材料的受控温度凝胶与目标 1 和 2 中追求的建筑设计目标相结合。该奖项反映了 NSF 的法定使命，并通过使用评估被认为值得支持。基金会的智力价值和更广泛的影响审查标准。

项目成果

Large Sequence-Defined Supramolecules Obtained by the DNA-Guided Assembly of Biohybrid Poly(phosphodiester)s

通过 DNA 引导的生物杂化聚磷酸二酯组装获得大序列定义的超分子

• DOI: 10.1021/acs.macromol.0c02581
• 发表时间: 2021-04
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Mondal, Tathagata;Nerantzaki, Maria;Flesch, Kevin;Loth, Capucine;Maaloum, Mounir;Cong, Yidan;Sheiko, Sergei S.;Lutz, Jean
• 通讯作者: Lutz, Jean

Super-soft, firm, and strong elastomers toward replication of tissue viscoelastic response

超软、坚固且坚固的弹性体，可复制组织粘弹性响应

• DOI: 10.1039/d2mh00844k
• 发表时间: 2022-09
• 期刊: Materials Horizons
• 影响因子: 13.3
• 作者: Dashtimoghadam, Erfan;Maw, Mitchell;Keith, Andrew N.;Vashahi, Foad;Kempkes, Verena;Gordievskaya, Yulia D.;Kramarenko, Elena Yu.;Bersenev, Egor A.;Nikitina, Evgeniia A.;Ivanov, Dimitri A.;et al
• 通讯作者: et al

Circular Upcycling of Bottlebrush Thermosets

洗瓶刷热固性材料的循环升级

• DOI: 10.1002/ange.202217941
• 发表时间: 2023-01
• 期刊: Angewandte Chemie
• 作者: Zhang, Daixuan;Vashahi, Foad;Dashtimoghadam, Erfan;Hu, Xiaobo;Wang, Claire J.;Garcia, Jessica;Bystrova, Aleksandra V.;Vatankhah‐Varnoosfaderani, Mohammad;Leibfarth, Frank A.;Sheiko, Sergei S.
• 通讯作者: Sheiko, Sergei S.

Secondary structure and stability of a gel‐forming tardigrade desiccation‐tolerance protein

凝胶形成缓步动物干燥耐受蛋白的二级结构和稳定性

• DOI: 10.1002/pro.4495
• 发表时间: 2022-11-06
• 期刊: Protein Science
• 影响因子: 8
• 作者: Jonathan Eicher;Julia A Brom;Shikun Wang;S. Sheiko;J. Atkin;G. Pielak
• 通讯作者: G. Pielak

Tissue‐Adaptive Materials with Independently Regulated Modulus and Transition Temperature

具有独立调节模量和转变温度的组织自适应材料

• DOI: 10.1002/adma.202005314
• 发表时间: 2020-11
• 期刊: Advanced Materials
• 影响因子: 29.4
• 作者: Zhang, Daixuan;Dashtimoghadam, Erfan;Fahimipour, Farahnaz;Hu, Xiaobo;Li, Qiaoxi;Bersenev, Egor A.;Ivanov, Dimitri A.;Vatankhah‐Varnoosfaderani, Mohammad;Sheiko, Sergei S.
• 通讯作者: Sheiko, Sergei S.