Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles

Abstract : Nanophase segregation of a bi-component thiol self-assembled monolayer is predicted using atomistic molecular dynamics simulations and experimentally confirmed. The simulations suggest the formation of domains rich in acid-terminated chains, on one hand, and of domains rich in amide-functionalized ethylene glycol oligomers, on the other hand. In particular, within the amide-ethylene glycol oligomers region, a key role is played by the formation of inter-chain hydrogen bonds. The predicted phase segregation is experimentally confirmed by the synthesis of 35 and 15 nm gold nanoparticles functionalized with several binary mixtures of ligands. An extensive study by transmission electron microscopy and electron tomography, using silica selective heterogeneous nucleation on acid-rich domains to provide electron contrast, supports simulations and highlights patchy nanoparticles with a trend towards Janus nano-objects depending on the nature of the ligands and the particle size. These results validate our computational platform as an effective tool to predict nanophase separation in organic mixtures on a surface and drive further exploration of advanced nanoparticle functionalization.
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ACS Nano, American Chemical Society, 2017, 11 (7), pp.7371-7381. 〈10.1021/acsnano.7b03616〉
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Santosh Kumar Meena, Claire Goldmann, Douga Nassoko, Mahamadou Seydou, Thomas Marchandier, et al.. Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles. ACS Nano, American Chemical Society, 2017, 11 (7), pp.7371-7381. 〈10.1021/acsnano.7b03616〉. 〈hal-01543644〉

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