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.

非技术概述活体组织在几乎恒定的水分数下无缝跨越从超软脑到超韧软骨的一系列机械性能的能力是独特的。相反，组织的合成类似物（即聚合物凝胶）目前不能在不影响其力学的情况下控制水量。 本文提出了一类基于瓶刷-大分子结构的新型聚合物材料，以实现对凝胶组成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，瓶刷结构引入了无数的侧链或“刷毛”，这些侧链或“刷毛”提供了额外的分子参数来调节柔软度而不改变水分数。此外，定制侧链末端的化学性质将使新的应用成为可能，例如用于组织模拟装置的增材制造的可编程和可注射材料。提出的新型聚合物凝胶将通过整合尖端聚合物化学，软物质物理学和新兴技术为跨学科研究提供充足的机会，这些技术可能会在许多应用中取得突破，如生物医学设备，组织工程支架和软机器人。本项目将解决三个基本挑战。首先，平衡溶胀比和凝胶的机械性能将分别与刷状网络的结构参数，如侧链长度和接枝密度相关。结构-溶胀-力学相关性的三角测量将提供对溶胀、柔软度和非线性机械响应的独立控制。例如，这将产生一系列前所未有的合成凝胶，具有相同的溶剂分数，但模量在几个数量级内变化。第二个目标是设计刷状介嵌段，其能够无溶剂注射仿组织弹性体。挑战在于将固化时间从几秒控制到几天，与完全固化的聚合物网络的机械性能分开。最后，目标1和2的成功实现将使一类基于热敏水凝胶的新型生物墨水材料成为可能，这种材料可以注入和3D打印具有明确定义的溶剂分数和机械性能的物体。这里的主要挑战是将印刷材料的受控温度凝胶化与目标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，并被认为值得通过使用基金会的知识价值和更广泛的影响审查标准进行评估来支持。

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
• 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-François
• 通讯作者: Lutz, Jean-François

Injectable non-leaching tissue-mimetic bottlebrush elastomers as an advanced platform for reconstructive surgery.

• DOI: 10.1038/s41467-021-23962-8
• 发表时间: 2021-06-25
• 期刊: Nature communications
• 影响因子: 16.6
• 作者: Dashtimoghadam E;Fahimipour F;Keith AN;Vashahi F;Popryadukhin P;Vatankhah-Varnosfaderani M;Sheiko SS
• 通讯作者: Sheiko SS

Tissue‐Adaptive Materials with Independently Regulated Modulus and Transition Temperature

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

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
• 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.

Brush Gels: Where Theory, Simulations, and Experiments Meet

• DOI: 10.1021/acs.macromol.2c01149
• 发表时间: 2022-08-18
• 期刊: MACROMOLECULES
• 影响因子: 5.5
• 作者: Jacobs, Michael;Vashahi, Foad;Dobrynin, Andrey V.
• 通讯作者: Dobrynin, Andrey V.