From experimental studies, it is well known that colloidal particles suspended in a near-critical binary solvent exhibit interesting aggregation phenomena, often associated with colloidal phase transitions and assumed to be driven by long-ranged solvent-mediated (SM) interactions (critical Casimir forces), set by the (diverging) correlation length of the solvent. We present the first simulation and theoretical study of an explicit model of a ternary mixture that mimics this situation. Both the effective SM pair interactions and the full ternary phase diagram are determined for Brownian disks suspended in an explicit two-dimensional supercritical binary liquid mixture. Gas-liquid and fluid-solid transitions are observed in a region that extends well away from criticality of the solvent reservoir. We discuss to what extent an effective pairpotential description can account for the phase behavior we observe. Our study provides a fresh perspective on how proximity to the critical point of the solvent reservoir might influence colloidal self-assembly. DOI: 10.1103/PhysRevLett.114.038301 PACS numbers: 82.70.Dd, 47.57.J−, 64.70.pv, 64.75.Xc Colloidal particles dispersed in a binary solvent mixture have an inherent preference for one of the two solvent species. This is reflected by preferential adsorption of the favored species on the colloid surface, leading to the development of adsorbed films. Such films can mediate an effective interaction between two colloidal particles which is remarkably sensitive to the thermodynamic state of the solvent. Close to the (demixing) critical point of the solvent, the adsorbed film thickness is determined by the correlation length ξ of the solvent [1], and, as first predicted by Fisher and de Gennes [2], the resulting solvent-mediated (SM) interactions are long ranged, with universal scaling properties. An analogy between the confinement of quantum fluctuations of the electromagnetic field [3] and that of thermal composition fluctuations in a near-critical binary solvent led to these (universal) SM forces being referred to as critical Casimir forces [4].Theoretical studies on near-critical fluids confined between a pair of infinitely large planar walls (representing two static large colloids) [4][5][6][7][8], along with direct experimental measurements of the Casimir force [9,10] between a colloid and a wall, have advanced our understanding of the nature of two-body SM interactions. Although experimental investigations of a suspension of colloids go back to the pioneering work of Beysens and Estève [11] (for a very recent experimental study, see [12]), the theory and computer simulation of such systems remain at a primitive stage. Here we use computer simulations of a simple model to understand the strength and range of the SM interactions and the resulting phase behavior of a dense colloidal suspension as a function of the thermodynamic state of the solvent. Computer simulation of colloids in an explicit molecular solvent with a bulk correlation length that diverges upon approac...

Like polypeptides, peptoids, or N‐substituted glycine oligomers, have intrinsic conformational preferences due to their amide backbones and close spacing of side chain substituents. However, the conformations that peptoids adopt are distinct from polypeptides due to several structural differences: the peptoid backbone is composed of tertiary amide bonds that have trans and cis conformers similar in energy, they lack a backbone hydrogen bond donor, and have an N‐substituent. To better understand how these differences manifest in actual peptoid structures, we analyzed 46 high quality, experimentally determined peptoid structures reported in the literature to extract their backbone conformational preferences. One hundred thirty‐two monomer dihedral angle pairs were compared to the calculated energy landscape for the peptoid Ramachandran plot, and were found to fall within the expected minima. Interestingly, only two regions of the backbone dihedral angles ϕ and ψ were found to be populated that are mirror images of each other. Furthermore, these two conformers are present in both cis and trans forms. Thus, there are four primary conformers that are sufficient to describe almost all known backbone conformations for peptoid oligomers, despite conformational constraints imposed by a variety of side chains, macrocyclization, or crystal packing forces. Because these conformers are predominant in peptoid structure, and are distinct from those found in protein secondary structures, we propose a simple naming system to aid in the description and classification of peptoid structure.

The conformations adopted by the molecular constituents of a supramolecular assembly influence its large-scale order. At the same time, the interactions made in assemblies by molecules can influence their conformations. Here we study this interplay in extended flat nanosheets made from nonnatural sequence-specific peptoid polymers. Nanosheets exist because individual polymers can be linear and untwisted, by virtue of polymer backbone elements adopting alternating rotational states whose twists oppose and cancel. Using molecular dynamics and quantum mechanical simulations, together with experimental data, we explore the design space of flat nanostructures built from peptoids. We show that several sets of peptoid backbone conformations are consistent with their being linear, but the specific combination observed in experiment is determined by a combination of backbone energetics and the interactions made within the nanosheet. Our results provide a molecular model of the peptoid nanosheet consistent with all available experimental data and show that its structure results from a combination of intra- and intermolecular interactions.

Peptoid nanosheets are supramolecular protein-mimetic materials that form from amphiphilic polypeptoids with aromatic and ionic side chains. Nanosheets have been studied at the nanometer scale, but the molecular structure has been difficult to probe. We report the use of C-C dipolar recoupling solid-state NMR measurements to reveal the configuration of backbone amide bonds selected by C isotopic labeling of adjacent α-carbons. Measurements on the same molecules in the amorphous state and in nanosheets revealed that amide bonds in the center of the amino block of peptoid (NaeNpe)-(NceNpe) (B28) favor the trans configuration in the amorphous state and the cis configuration in the nanosheet. This unexpected result contrasts with previous NMR and theoretical studies of short solvated peptoids. Furthermore, examination of the amide bond at the junction of the two charged blocks within B28 revealed a mixture of both cis and trans configurational states, consistent with the previously predicted brickwork-like intermolecular organization.