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The interplay of nanointerface curvature and calcium binding in weak polyelectrolyte-coated nanoparticles†
Biomaterials Science ( IF 5.8 ) Pub Date : 2018-03-15 00:00:00 , DOI: 10.1039/c8bm00135a
Rikkert J Nap 1 , Estefania Gonzalez Solveyra , Igal Szleifer
Affiliation  

When engineering nanomaterials for application in biological systems, it is important to understand how multivalent ions, such as calcium, affect the structural and chemical properties of polymer-modified nanoconstructs. In this work, a recently developed molecular theory was employed to study the effect of surface curvature on the calcium-induced collapse of end-tethered weak polyelectrolytes. In particular, we focused on cylindrical and spherical nanoparticles coated with poly(acrylic acid) in the presence of different amounts of Ca2+ ions. We describe the structural changes that grafted polyelectrolytes undergo as a function of calcium concentration, surface curvature, and morphology. The polymer layers collapse in aqueous solutions that contain sufficient amounts of Ca2+ ions. This collapse, due to the formation of calcium bridges, is not only controlled by the calcium ion concentration but also strongly influenced by the curvature of the tethering surface. The transition from a swollen to a collapsed layer as a function of calcium concentration broadens and shifts to lower amounts of calcium ions as a function of the radius of cylindrical and spherical nanoparticles. The results show how the interplay between calcium binding and surface curvature governs the structural and functional properties of the polymer molecules. This would directly impact the fate of weak polyelectrolyte-coated nanoparticles in biological environments, in which calcium levels are tightly regulated. Understanding such interplay would also contribute to the rational design and optimization of smart interfaces with applications in, e.g., salt-sensitive and ion-responsive materials and devices.

中文翻译:


弱聚电解质涂层纳米粒子中纳米界面曲率和钙结合的相互作用†



在设计用于生物系统的纳米材料时,了解多价离子(例如钙)如何影响聚合物改性纳米结构的结构和化学性质非常重要。在这项工作中,采用最近发展的分子理论来研究表面曲率对钙诱导的末端束缚弱聚电解质塌陷的影响。我们特别关注在不同量的 Ca 2+离子存在下涂覆有聚丙烯酸的圆柱形和球形纳米粒子。我们描述了接枝聚电解质所经历的结构变化作为钙浓度、表面曲率和形态的函数。聚合物层在含有足够量Ca 2+离子的水溶液中塌陷。由于钙桥的形成,这种塌陷不仅受到钙离子浓度的控制,而且还受到束缚表面曲率的强烈影响。作为钙浓度的函数,从膨胀层到塌陷层的转变变宽,并且随着圆柱形和球形纳米粒子的半径的变化,钙离子的量减少。结果显示钙结合和表面曲率之间的相互作用如何控制聚合物分子的结构和功能特性。这将直接影响弱聚电解质涂层纳米颗粒在生物环境中的命运,在生物环境中钙水平受到严格调节。了解这种相互作用也将有助于智能界面的合理设计和优化,以及在盐敏感和离子响应材料和设备中的应用。
更新日期:2018-03-15
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