Quantified Binding Scale of Competing Ligands at the Surface of Gold Nanoparticles: The Role of Entropy and Intermolecular Forces

Goldmann, Claire; Ribot, François; Peiretti, Leonardo Federico; Quaino, Paola; Tielens, Frederik; Sánchez, Clément; Chanéac, Corinne; Portehault, David

doi:10.1002/smll.201604028

Cited by 24 publications

(26 citation statements)

References 71 publications

(199 reference statements)

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“…22 In the TegA/MHA system intermolecular H-bonds between amide groups of neighboring TegA ligands ( Figure 5) 23,45 must drive phase separation in the ligand shell, as expected from simulations (Figure 3a).…”

Section: Since Our Partially (Figures 3a-d) and Fully (Figures 3e-h) mentioning

confidence: 54%

“…23 Thus, computational approaches may help identifying driving forces to guide the design of new dissymetric, Janus or patchy nanoparticles by the rational choice of reagents and synthesis conditions. Coarse-grain molecular dynamics (MD), [24][25][26][27] Atomistic MD, 28 and Monte Carlo simulations, 28 have identified conformational entropic effects as the driving force for nanophase separation in binary thiol SAMs on gold nanoparticles, provided that the two kinds of molecules are not miscible and have sufficiently different chain lengths.…”

Section: Introductionmentioning

confidence: 99%

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Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles

et al. 2017

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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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Section: Since Our Partially (Figures 3a-d) and Fully (Figures 3e-h) mentioning

confidence: 54%

Section: Introductionmentioning

confidence: 99%

Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles

et al. 2017

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“…2.2 eV). [82,83] This leads us to conclude that the S-Au bond is sensitive to the hybridization state if the carbon atom bound to the sulphur atom.…”

Section: Discussionmentioning

confidence: 95%

Rationalizing the formation of binary mixed thiol self-assembled monolayers

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Goldmann

et al. 2017

Materials Today Chemistry

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International audiencePeriodic DFT-D calculations are used to decipher the role of intermolecular forces on the stability of mixed linear thiol self-assembled monolayers (SAMs) on Au(111) and compared with experiment. The interaction energy is rationalized by quantifying its different contributions. The inter-chain interaction energy is shown to be in direct relation with the surface reconstruction and the formation of adatoms. The stability of the mixed SAM systems is predicted by calculations and validated with experiments. In order to describe predictively the segregation of binary thiol mixtures adsorption on Au surfaces a segregation descriptor is defined. This procedure is a promising step forward in the prediction of segregated SAMs leading to future functional nanomaterials, including Janus or patchy nanoparticles for optics, formulation and self-assembled patterns

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“…In situ characterizations, like NAP-XPS and TEM 31 will be pertinent in this context, but again the example of gold particles draws future guidelines to understand hybrid interfaces, especially the organic layer composition and the ligands distribution, by Nuclear Magnetic Resonance 56 and electron tomography 57 coupled to Density Functional Theory calculations and molecular dynamic simulations. 56,57…”

Section: Understanding and Tuning Surface Statesmentioning

confidence: 99%

Beyond the Compositional Threshold of Nanoparticle-Based Materials

et al. 2018

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The design of inorganic nanoparticles relies strongly on the knowledge from solid-state chemistry not only for characterization techniques, but also and primarily for choosing the systems that will yield the desired properties. The range of inorganic solids reported and studied as nanoparticles is however strikingly narrow when compared to the solid-state chemistry portfolio of bulk materials. Efforts to enlarge the collection of inorganic particles are becoming increasingly important for three reasons. First, they can yield materials more performing than current ones for a range of fields including biomedicine, optics, catalysis, and energy. Second, looking outside the box of common compositions is a way to target original properties or to discover genuinely new behaviors. The third reason lies in the path followed to reach these novel nano-objects: exploration and setup of new synthetic approaches. Indeed, willingness to access original nanoparticles faces a synthetic challenge: how to reach nanoparticles of solids that originally belong to the realm of solid-state chemistry and its typical protocols at high temperature? To answer this question, alternative reaction pathways must be sought, which may in turn provide tracks for new, untargeted materials. The corresponding strategies require limiting particle growth by confinement at high temperatures or by decreasing the synthesis temperature. Both approaches, especially the latter, provide a nice playground to discover metastable solids never reported before. The aim of this Account is to raise attention to the topic of the design of new inorganic nanoparticles. To do so, we take the perspective of our own work in the field, by first describing synthetic challenges and how they are addressed by current protocols. We then use our achievements to highlight the possibilities offered by new nanomaterials and to introduce synthetic approaches that are not in the focus of recent literature but hold, in our opinion, great promise. We will span methods of low temperature "chimie douce" aqueous synthesis coupled to microwave heating, sol-gel chemistry and processing coupled to solid state reactions, and then molten salt synthesis. These protocols pave the way to metastable low valence oxyhydroxides, vanadates, perovskite oxides, boron carbon nitrides, and metal borides, all obtained at the nanoscale with structural and morphological features differing from "usual" nanomaterials. These nano-objects show original properties, from sensing, thermoelectricity, charge and spin transports, photoluminescence, and catalysis, which require advanced characterization of surface states. We then identify future trends of synthetic methodologies that will merit further attention in this burgeoning field, by emphasizing the importance of unveiling reaction mechanisms and coupling experiments with modeling.

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Quantified Binding Scale of Competing Ligands at the Surface of Gold Nanoparticles: The Role of Entropy and Intermolecular Forces

Cited by 24 publications

References 71 publications

Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles

Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles

Rationalizing the formation of binary mixed thiol self-assembled monolayers

Beyond the Compositional Threshold of Nanoparticle-Based Materials

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