Peptide Stereocomplexation Orchestrates Supramolecular Assembly of Hydrogel Biomaterials
Peptide Stereocomplexation Orchestrates Supramolecular Assembly of Hydrogel Biomaterials
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DOI：
10.1021/jacs.3c04872
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发表时间：
2023-08-11
影响因子：
15
通讯作者：
Letteri, Rachel A.
中科院分区：
文献类型：
--
作者：
Duti, Israt Jahan;Florian, Jonathan R.;Letteri, Rachel A.
立体络合，或互补立体规则大分子之间的特定相互作用，正在蓬勃发展，作为一种越来越有影响力的设计工具，对材料结构和性能进行精密控制。由于聚合物的立体络合作用在力学、形态学和降解方面产生了明显的变化，我们试图利用立体络合作用来调节肽基生物材料的这些性质。我们发现，混合五肽l-和d-KYFIL触发双重的机械和形态的transformationfrom硬纤维水凝胶到不太硬的网络板，鲜明对比以前的报告，混合l-和d-肽产生更硬的纤维水凝胶比单独的成分。KYFIL在磷酸盐缓冲盐水中从缠结成水凝胶的纤维到不能缠结的板的形态转变解释了伴随的机械转变。此外，共混物屏蔽l-KYFIL从蛋白水解降解，生产材料具有可比的蛋白水解稳定性的d-KYFIL，但具有不同的二维板形态，在生物材料中可以促进独特的治疗释放曲线和细胞行为。为了证实这些形态、机械和稳定性的变化是由于聚合物立体络合作用中分子堆积的差异引起的，我们获得了X-射线衍射图，它显示l-和d-KYFIL是无定形的，它们的混合物是结晶的。我们的研究结果突出了分子细节的作用，如肽序列，在determiningthe物质的性质所产生的立体络合。展望未来，立体络合能够协调超分子组装和调整应用关键特性，将立体化学作为一个引人注目的设计考虑因素。
Stereocomplexation, or specific interactions among complementarystereoregular macromolecules, is burgeoning as an increasingly impactfuldesign tool, exerting exquisite control of material structure andproperties. Since stereocomplexation of polymers produces remarkabletransformations in mechanics, morphology, and degradation, we soughtto leverage stereocomplexation to tune these properties in peptide-basedbiomaterials. We found that blending the pentapeptides l-and d-KYFIL triggers dual mechanical and morphological transformationsfrom stiff fibrous hydrogels into less stiff networks of plates, starklycontrasting prior reports that blending l- and d-peptides produces stiffer fibrous hydrogels than the individualconstituents. The morphological transformation of KYFIL in phosphate-bufferedsaline from fibers that entangle into hydrogels to plates that cannotentangle explains the accompanying mechanical transformation. Moreover,the blends shield l-KYFIL from proteolytic degradation, producingmaterials with comparable proteolytic stability to d-KYFILbut with distinct 2D plate morphologies that in biomaterials may promoteunique therapeutic release profiles and cell behavior. To confirmthat these morphological, mechanical, and stability changes arisefrom differences in molecular packing as in polymer stereocomplexation,we acquired X-ray diffraction patterns, which showed l- and d-KYFIL to be amorphous and their blends to be crystalline.Stereocomplexation is particularly apparent in pure water, where l- and d-KYFIL are soluble random coils, and theirblends form & beta;-sheets and gel within minutes. Our results highlightthe role of molecular details, such as peptide sequence, in determiningthe material properties resulting from stereocomplexation. Lookingforward, the ability of stereocomplexation to orchestrate supramolecularassembly and tune application-critical properties champions stereochemistryas a compelling design consideration.