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Authors
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Li, C.-W.; Merlitz, H.; Sommer, J.-U.
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Title
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Polymers grafted onto capsular nanoparticles in a good solvent: Conformational properties and distribution of grafting points
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Date
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12.08.2025
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Number
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0
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Abstract
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We investigate the structural characteristics of polymer-decorated capsular nanoparticles (PDNPs) in good solvents using molecular dynamics (MD) simulations and theoretical modeling. The capsular substrate consists of two hemispherical tips (radius R) connected by a cylindrical segment of length L. We model the commonly employed grafting-to process by allowing movable grafting points on the particle surface, which leads to a grafting density distribution that varies in a geometry-dependent manner. The grafting density progressively decreases from the spherical tips toward the cylindrical midsection, and in the limiting case of highly elongated particles, the grafting density on the spherical tips can reach up to twice the value in the cylindrical region. The global monomer density profile follows a geometry-dependent scaling law c(r) ∼ σ2/3(r/R)α, where the exponent α is given by an L-dependent function. Two mechanisms define the local grafting density on substrates of varying curvature: the steric repulsion between neighboring chains, which are taken into account by the conventional blob-based scaling approaches and which dominate at high monomer concentrations, and the substrate-related half-space restriction, which affects the conformational entropy of each individual chain and which is of relevance at low densities. We separate and investigate both effects by simulating phantom chains and observing their distributions on the PDNP. Along with our generalized mean-field description of these PDNPs for various setups, our findings establish a unified framework for understanding PDNP configurations and provide design principles for anisotropic nanomaterials with spatially programmable surface properties, such as self-assembling building blocks.
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Publisher
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American Chemical Society
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Wikidata
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Citation
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Macromolecules 58 (2025) 8524-8535
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DOI
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https://doi.org/10.1021/acs.macromol.5c01108
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