Surface-Cross-linked Protein-like Single-Chain Nanoparticle Globules Unexpectedly Stabilized with a Low Cross-linking Degree,Macromolecules

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Surface-Cross-linked Protein-like Single-Chain Nanoparticle Globules Unexpectedly Stabilized with a Low Cross-linking Degree
Macromolecules ( IF 5.1 ) Pub Date : 2024-01-13 , DOI: 10.1021/acs.macromol.3c01863
Lei Zhang ₁ , Xu-Ze Zhang ₁ , Jia-Tong Lyu ₂ , Lin-Xiuzi Yu ₁ , Chun-Yu Wang ₁ , Zhao-Yan Sun ₃ , Zhong-Yuan Lu ₁ , Hu-Jun Qian ₁

Affiliation

Single-chain nanoparticles (SCNPs) are an emerging new nanomaterial with promising potential for exhibiting compactly collapsed globular nanostructures and associated functions, like proteins. However, the state-of-the-art synthesis approaches often result in SCNPs with diverse morphologies and loosely packed characteristics, even with an ample presence of cross-linkers, resembling sparse structures found in intrinsically disordered proteins. Herein, we present a facile strategy to fabricate protein-like compact SCNP globules using a low content of solvophilic photoreactive agents in a single-component poor solvent via flow photochemistry. Photoreactive agents in our system serve a dual purpose: acting as stabilizing agents that decorate the surface of the precollapsed precursor globules in the poor solvent and cross-linking with neighboring segments in situ upon UV irradiation on the globule surfaces. These cross-linked globules become effectively locked and remain stable when transferred into a good solvent. Computer simulations demonstrate that surface cross-linking reactions primarily occur between cross-linkers and neighboring monomers positioned at long contour distances along the chain backbone. This mechanism locks up the precollapsed protein-like SCNP globules with high efficiency; an extremely low cross-linker content of 1.6 mol % can result in an obvious reduction in molecular size. Small-angle X-ray scattering (SAXS) measurements also confirm the formation of compactly collapsed globule structures. Moreover, by varying the UV irradiation time, the degree of collapse in the SCNPs can be precisely controlled. The residual cross-linkers on the surface render the formed SCNPs reactive, thus allowing for further polymerization into hierarchical multifunctional self-assembly structures.

中文翻译：

表面交联的类蛋白质单链纳米颗粒小球意外地以低交联度稳定

单链纳米粒子（SCNP）是一种新兴的纳米材料，具有展现紧密塌陷的球状纳米结构和相关功能（如蛋白质）的巨大潜力。然而，最先进的合成方法通常会产生具有不同形态和松散堆积特征的 SCNP，即使存在大量交联剂，类似于本质上无序的蛋白质中发现的稀疏结构。在此，我们提出了一种简便的策略，通过流动光化学，在单组分不良溶剂中使用低含量的亲溶剂性光反应剂来制造类蛋白质致密 SCNP 球。我们系统中的光反应剂具有双重目的：充当稳定剂，装饰不良溶剂中预塌陷的前体小球的表面，并在小球表面上的紫外线照射下与相邻片段原位交联。当转移到良溶剂中时，这些交联的小球被有效锁定并保持稳定。计算机模拟表明，表面交联反应主要发生在交联剂和沿着链主链位于长轮廓距离处的相邻单体之间。该机制高效锁定预塌陷的类蛋白 SCNP 小球； 1.6 mol% 的极低交联剂含量可导致分子尺寸明显减小。小角 X 射线散射 (SAXS) 测量也证实了致密塌缩球状结构的形成。此外，通过改变紫外线照射时间，可以精确控制 SCNP 的塌陷程度。表面上残留的交联剂使形成的 SCNP 具有反应性，从而允许进一步聚合成分层多功能自组装结构。

更新日期：2024-01-13

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