Dynamic Implications of Noncovalent Interactions in Amphiphilic Single-Chain Polymer Nanoparticles,ACS Macro Letters

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Dynamic Implications of Noncovalent Interactions in Amphiphilic Single-Chain Polymer Nanoparticles
ACS Macro Letters ( IF 5.1 ) Pub Date : 2024-07-03 , DOI: 10.1021/acsmacrolett.4c00269
Peter A Dykeman-Bermingham ₁ , Laura R Stingaciu ₂ , Changwoo Do ₂ , Abigail S Knight ₁

Affiliation

Single-chain polymer nanoparticles (SCNPs) combine the chemical diversity of synthetic polymers with the intricate structure of biopolymers, generating versatile biomimetic materials. The mobility of polymer chain segments at length scales similar to secondary structural elements in proteins is critical to SCNP structure and thus function. However, the influence of noncovalent interactions used to form SCNPs (e.g., hydrogen-bonding and biomimetic secondary-like structure) on these conformational dynamics is challenging to quantitatively assess. To isolate the effects of noncovalent interactions on SCNP structure and conformational dynamics, we synthesized a series of amphiphilic copolymers containing dimethylacrylamide and monomers capable of forming these different interactions: (1) di(phenylalanine) acrylamide that forms intramolecular β-sheet-like cross-links, (2) phenylalanine acrylamide that forms hydrogen-bonds but lacks a defined local structure, and (3) benzyl acrylamide that has the lowest propensity for hydrogen-bonding. Each SCNP formed folded structures comparable to those of intrinsically disordered proteins, as observed by size exclusion chromatography and small angle neutron scattering. The dynamics of these polymers, as characterized by a combination of dynamic light scattering and neutron spin echo spectroscopy, was well described using the Zimm with internal friction (ZIF) model, highlighting the role of each noncovalent interaction to additively restrict the internal relaxations of SCNPs. These results demonstrate the utility of local scale interactions to control SCNP polymer dynamics, guiding the design of functional biomimetic materials with refined binding sites and tunable kinetics.

中文翻译：

两亲性单链聚合物纳米粒子中非共价相互作用的动态影响

单链聚合物纳米颗粒 (SCNP) 将合成聚合物的化学多样性与生物聚合物的复杂结构相结合，产生多功能仿生材料。聚合物链段在长度尺度上的移动性与蛋白质中的二级结构元件相似，对于 SCNP 结构和功能至关重要。然而，用于形成 SCNP 的非共价相互作用（例如氢键和仿生二级结构）对这些构象动力学的影响很难定量评估。为了分离非共价相互作用对 SCNP 结构和构象动力学的影响，我们合成了一系列含有二甲基丙烯酰胺和能够形成这些不同相互作用的单体的两亲性共聚物：（1）二（苯丙氨酸）丙烯酰胺，形成分子内 β-片状交叉-链接，（2）苯丙氨酸丙烯酰胺形成氢键但缺乏明确的局部结构，（3）苯甲基丙烯酰胺具有最低的氢键倾向。通过尺寸排阻色谱和小角中子散射观察到，每个 SCNP 形成的折叠结构与本质上无序的蛋白质相当。这些聚合物的动力学，以动态光散射和中子自旋回波光谱相结合为特征，使用 Zimm 内摩擦 (ZIF) 模型得到了很好的描述，强调了每种非共价相互作用在额外限制 SCNP 内部弛豫方面的作用。这些结果证明了局部尺度相互作用在控制 SCNP 聚合物动力学方面的实用性，指导具有精细结合位点和可调动力学的功能仿生材料的设计。

更新日期：2024-07-03

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