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The interplay of nanointerface curvature and calcium binding in weak polyelectrolyte-coated nanoparticles

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Abstract

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.

Graphical abstract: The interplay of nanointerface curvature and calcium binding in weak polyelectrolyte-coated nanoparticles

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Publication details

The article was received on 03 Feb 2018, accepted on 02 Mar 2018 and first published on 15 Mar 2018


Article type: Paper
DOI: 10.1039/C8BM00135A
Citation: Biomater. Sci., 2018, Advance Article
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    The interplay of nanointerface curvature and calcium binding in weak polyelectrolyte-coated nanoparticles

    R. J. Nap, E. Gonzalez Solveyra and I. Szleifer, Biomater. Sci., 2018, Advance Article , DOI: 10.1039/C8BM00135A

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