Probing the Solvent-Assisted Nucleation Pathway in Chemical Self-Assembly

Jonkheijm, Pascal; Schoot, Paul van der; Schenning, Albertus P. H. J.; Meijer, E. W.

doi:10.1126/science.1127884

Cited by 852 publications

(749 citation statements)

References 41 publications

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“…59,60 The solvent has also been found to play an important role in the supramolecular assembly of conjugated molecules into nanofibers. 61 The interaction of nanoparticles with biological materials is an important situation where this effect arises. Hence, the general problem of how the medium in which such particles are placed generates effective interparticle interactions merits further investigation.…”

Section: Discussionmentioning

confidence: 99%

Model for reversible nanoparticle assembly in a polymer matrix

Rahedi

Douglas

Starr

2008

The Journal of Chemical Physics

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The clustering of nanoparticles ͑NPs͒ in solutions and polymer melts depends sensitively on the strength and directionality of the NP interactions involved, as well as the molecular geometry and interactions of the dispersing fluids. Since clustering can strongly influence the properties of polymer-NP materials, we aim to better elucidate the mechanism of reversible self-assembly of highly symmetric NPs into clusters under equilibrium conditions. Our results are based on molecular dynamics simulations of icosahedral NP with a long-ranged interaction intended to mimic the polymer-mediated interactions of a polymer-melt matrix. To distinguish effects of polymer-mediated interactions from bare NP interactions, we compare the NP assembly in our coarse-grained model to the case where the NP interactions are purely short ranged. For the "control" case of NPs with short-ranged interactions and no polymer matrix, we find that the particles exhibit ordinary phase separation. By incorporating physically plausible long-ranged interactions, we suppress phase separation and qualitatively reproduce the thermally reversible cluster formation found previously in computations for NPs with short-ranged interactions in an explicit polymer-melt matrix. We further characterize the assembly process by evaluating the cluster properties and the location of the self-assembly transition. Our findings are consistent with a theoretical model for equilibrium clustering when the particle association is subject to a constraint. In particular, the density dependence of the average cluster mass exhibits a linear concentration dependence, in contrast to the square root dependence found in freely associating systems. The coarse-grained model we use to simulate NP in a polymer matrix shares many features of potentials used to model colloidal systems. The model should be practically valuable for exploring factors that control the dispersion of NP in polymer matrices where explicit simulation of the polymer matrix is too time consuming.

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Section: Discussionmentioning

confidence: 99%

Model for reversible nanoparticle assembly in a polymer matrix

Rahedi

Douglas

Starr

2008

The Journal of Chemical Physics

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“…The coupling between nanotube self-assembly and intermolecular interactions with (and between) encapsulated solvent molecules also provides an unprecedented insight into how small differences in intermolecular interactions have a large impact on supramolecular assemblies and highlights the important role of solvent therein, a role that so far has not received the attention that it merits in the experimental and theoretical literature. 11 The compound we focus attention on belongs to a class of bisureas known to self-assemble, through intermolecular hydrogen bonding, into filaments below a polymerization temperature T*, and into narrow tubes for temperatures T ≤ T** ≤ T* . 12,13 While the polymerization of monomers into filaments is cooperative, the filament−tube transition at T** is even sharper and resembles a phase transition.…”

Section: ■ Introductionmentioning

confidence: 99%

Probing Weak Intermolecular Interactions in Self-Assembled Nanotubes

Bouteiller

Schoot

2012

J. Am. Chem. Soc.

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Extreme confinement affects the physical properties of fluids, but little quantitative data is available. We report on studies of a bisurea compound that self-assembles into nanotubes to probe solvent confinement on the angstrom scale. By applying a statistical model to calorimetric data obtained on solvent mixtures, we show that the thermodynamic stability of the nanotubes is an extremely sensitive function of the solvent composition because solvent interactions inside and outside of the nanotubes are different. We are able to measure energetic effects as small as 0.01 kT and relate them to the differences in molecular structure of the solvents.

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“…The gels were investigated after a period of 24 h. This type of process is frequently required for the formation of gels as it provides the molecular building blocks with sufficient energy to overcome the kinetic barrier to self-assembly. 24 Controlled curing of the gel during cooling ensures the formation of soft materials with reproducible properties. …”

Section: Thermal Stabilities and Ir Studiesmentioning

confidence: 99%

Exploring Molecular Recognition Pathways within a Family of Gelators with Different Hydrogen Bonding Motifs.

et al. 2007

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General rights Copyright for the publications made accessible via the Queen's University Belfast Research Portal is retained by the author(s) and / or other copyright owners and it is a condition of accessing these publications that users recognise and abide by the legal requirements associated with these rights. AbstractWe report the synthesis of a family of gelators in which alkyl chains are connected to the amino groups of L-lysine methyl ester using a range of different hydrogen bonding linking groups (carbamate, amide, urea, thiourea and diacylhydrazine) using simple synthetic methodology based on isocyanate or acid chloride chemistry. The ability of these compounds to gelate organic solvents such as toluene or cyclohexane can be directly related to the ability of the linking group to form intermolecular hydrogen bonds. In general terms, the ability to structure solvents can be considered as:thiourea

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Probing the Solvent-Assisted Nucleation Pathway in Chemical Self-Assembly

Cited by 852 publications

References 41 publications

Model for reversible nanoparticle assembly in a polymer matrix

Model for reversible nanoparticle assembly in a polymer matrix

Probing Weak Intermolecular Interactions in Self-Assembled Nanotubes

Exploring Molecular Recognition Pathways within a Family of Gelators with Different Hydrogen Bonding Motifs.

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