Ice friction at the nanoscale.

The origin of ice slipperiness has been a matter of great controversy for more than a century, but an atomistic understanding of ice friction is still lacking. Here, we perform computer simulations of an atomically smooth substrate sliding on ice. In a large temperature range between 230 and 266 K, hydrophobic sliders exhibit a premelting layer similar to that found at the ice/air interface. On the contrary, hydrophilic sliders show larger premelting and a strong increase of the first adsorption layer. The nonequilibrium simulations show that premelting films of barely one-nanometer thickness are sufficient to provide a lubricating quasi-liquid layer with rheological properties similar to bulk undercooled water. Upon shearing, the films display a pattern consistent with lubricating Couette flow, but the boundary conditions at the wall vary strongly with the substrate's interactions. Hydrophobic walls exhibit large slip, while hydrophilic walls obey stick boundary conditions with small negative slip. By compressing ice above atmospheric pressure, the lubricating layer grows continuously, and the rheological properties approach bulk-like behavior. Below 260 K, the equilibrium premelting films decrease significantly. However, a very large slip persists on the hydrophobic walls, while the increased friction on hydrophilic walls is sufficient to melt ice and create a lubrication layer in a few nanoseconds. Our results show that the atomic-scale frictional behavior of ice is a combination of spontaneous premelting, pressure melting, and frictional heating.

Tuneable helices of plasmonic nanoparticles using liquid crystal templates: molecular dynamics investigation of an unusual odd-even effect in liquid crystalline dimers.

Liquid crystalline (LC) dimers formed helical nanofilaments depending on the parity of the alkyl linker, revealing an unusual odd-even effect. Molecular dynamics simulations were used to investigate the observed tendency. Elongation of the linker translates to an increase of the pitch of the helices, which allows achieving tuneable helical assemblies of Au nanoparticles doped to the LC matrix. The impact of the tuneable pitch of helices on the chiral optical properties of composites was investigated with full-wave simulations based on the T-matrix method.

How to design an icosahedral quasicrystal through directional bonding.

Icosahedral quasicrystals (IQCs) are materials that exhibit long-range order but lack periodicity in any direction. Although IQCs were the first reported quasicrystals1, they have been experimentally observed only in metallic alloys2, not in other materials. By contrast, quasicrystals with other symmetries (particularly dodecagonal) have now been found in several soft-matter systems3-5. Here we introduce a class of IQCs built from model patchy colloids that could be realized experimentally using DNA origami particles. Our rational design strategy leads to systems that robustly assemble in simulations into a target IQC through directional bonding. This is illustrated for both body-centred and primitive IQCs, with the simplest systems involving just two particle types. The key design feature is the geometry of the interparticle interactions favouring the propagation of an icosahedral network of bonds, despite this leading to many particles not being fully bonded. As well as furnishing model systems in which to explore the fundamental physics of IQCs, our approach provides a potential route towards functional quasicrystalline materials.

How ice grows from premelting films and water droplets.

Close to the triple point, the surface of ice is covered by a thin liquid layer (so-called quasi-liquid layer) which crucially impacts growth and melting rates. Experimental probes cannot observe the growth processes below this layer, and classical models of growth by vapor deposition do not account for the formation of premelting films. Here, we develop a mesoscopic model of liquid-film mediated ice growth, and identify the various resulting growth regimes. At low saturation, freezing proceeds by terrace spreading, but the motion of the buried solid is conveyed through the liquid to the outer liquid-vapor interface. At higher saturations water droplets condense, a large crater forms below, and freezing proceeds undetectably beneath the droplet. Our approach is a general framework that naturally models freezing close to three phase coexistence and provides a first principle theory of ice growth and melting which may prove useful in the geosciences.

Surface phase transitions and crystal habits of ice in the atmosphere.

With climate modeling predicting a raise of at least 2°C by year 2100, the fate of ice has become a serious concern, but we still do not understand how ice grows (or melts). In the atmosphere, crystal growth rates of basal and prism facets exhibit an enigmatic temperature dependence and crossover up to three times in a range between 0° and -40°. Here, we use large-scale computer simulations to characterize the ice surface and identify a sequence of previously unidentified phase transitions on the main facets of ice crystallites. Unexpectedly, we find that as temperature is increased, the crystal surface transforms from a disordered phase with proliferation of steps to a smooth phase with small step density. This causes the anomalous increase of step free energies and provides the long sought explanation for the enigmatic crossover of snow crystal growth rates found in the atmosphere.

Micelle-directed chiral seeded growth on anisotropic gold nanocrystals.

Surfactant-assisted seeded growth of metal nanoparticles (NPs) can be engineered to produce anisotropic gold nanocrystals with high chiroptical activity through the templating effect of chiral micelles formed in the presence of dissymmetric cosurfactants. Mixed micelles adsorb on gold nanorods, forming quasihelical patterns that direct seeded growth into NPs with pronounced morphological and optical handedness. Sharp chiral wrinkles lead to chiral plasmon modes with high dissymmetry factors (~0.20). Through variation of the dimensions of chiral wrinkles, the chiroptical properties can be tuned within the visible and near-infrared electromagnetic spectrum. The micelle-directed mechanism allows extension to other systems, such as the seeded growth of chiral platinum shells on gold nanorods. This approach provides a reproducible, simple, and scalable method toward the fabrication of NPs with high chiral optical activity.

Rounded Layering Transitions on the Surface of Ice.

Understanding the wetting properties of premelting films requires knowledge of the film's equation of state, which is not usually available. Here we calculate the disjoining pressure curve of premelting films and perform a detailed thermodynamic characterization of premelting behavior on ice. Analysis of the density profiles reveals the signature of weak layering phenomena, from one to two and from two to three water molecular layers. However, disjoining pressure curves, which closely follow expectations from a renormalized mean field liquid state theory, show that there are no layering phase transitions in the thermodynamic sense along the sublimation line. Instead, we find that transitions at mean field level are rounded due to capillary wave fluctuations. We see signatures that true first order layering transitions could arise at low temperatures, for pressures between the metastable line of water-vapor coexistence and the sublimation line. The extrapolation of the disjoining pressure curve above water-vapor saturation displays a true first order phase transition from a thin to a thick film consistent with experimental observations.

Structure and water attachment rates of ice in the atmosphere: role of nitrogen.

In this work we perform computer simulations of the ice surface in order to elucidate the role of nitrogen in the crystal growth rates and crystal habits of snow in the atmosphere. In pure water vapor at temperatures typical of ice crystal formation in cirrus clouds, we find that basal and primary prismatic facets exhibit a layer of premelted ice, with thickness in the subnanometer range. For partial pressures of 1 bar, well above the expected values in the troposphere, we find that only small amounts of nitrogen are adsorbed. The adsorption takes place onto the premelted surface, and hardly any nitrogen dissolves within the premelting film. The premelting film thickness does not change either. We quantify the resulting change of the ice/vapor surface tension to be in the hundredth of mN m-1 and find that the structure of the pristine ice surface is not changed in a significant manner. We perform a trajectory analysis of colliding water molecules, and find that the attachment rates from direct ballistic collision are very close to unity irrespective of the nitrogen pressure. Nitrogen is however at sufficient density to deflect a fraction of trajectories with smaller distance than the mean free path. Our results show explicitly that the reported differences in growth rates measured in pure water vapor and a controlled nitrogen atmosphere are not related to a significant disruption of the ice surface due to nitrogen adsorption. On the contrary, we show clearly from our trajectory analysis that nitrogen slows down the crystal growth rates due to collisions between water molecules with bulk nitrogen gas. This clarifies the long standing controversy of the role of inert gases on crystal growth rates and demonstrates their influence is solely related to the diffusion limited flow of water vapor across the gas phase.

Disconnecting Symmetry Breaking from Seeded Growth for the Reproducible Synthesis of High Quality Gold Nanorods.

One of the major difficulties hindering the widespread application of colloidal anisotropic plasmonic nanoparticles is the limited robustness and reproducibility of multistep synthetic methods. We demonstrate herein that the reproducibility and reliability of colloidal gold nanorod (AuNR) synthesis can be greatly improved by disconnecting the symmetry-breaking event from the seeded growth process. We have used a modified silver-assisted seeded growth method in the presence of the surfactant hexadecyltrimethylammonium bromide and n-decanol as a co-surfactant to prepare small AuNRs in high yield, which were then used as seeds for the growth of high quality AuNR colloids. Whereas the use of n-decanol provides a more-rigid micellar system, the growth on anisotropic seeds avoids sources of irreproducibility during the symmetry breaking step, yielding uniform AuNR colloids with narrow plasmon bands, ranging from 600 to 1270 nm, and allowing the fine-tuning of the final dimensions. This method provides a robust route for the preparation of high quality AuNR colloids with tunable morphology, size, and optical response in a reproducible and scalable manner.

Nucleation of pseudo hard-spheres and dumbbells at moderate metastability: appearance of A15 Frank-Kasper phase at intermediate elongations.

Crystal nucleation of repulsive hard-dumbbells from the sphere to the two tangent spheres limit is investigated at moderately high metastability by brute-force molecular dynamics simulations. Nucleation rates are in good agreement with previous simulations of hard-spheres and dumbbells. Icosahedral structures formed by twinned face-centred-cubic tetrahedra sharing five-fold symmetry axes and icosahedral centers are often found in spheres and dumbbells with either small (L/σ = 0.1 and 0.2) and large (L/σ = 1) elongations. These structures are incompatible with long range crystalline order but are able to survive up to quite large sizes. In contrast, at intermediate elongations (L/σ = 0.3), corresponding roughly to the bond length of molecular nitrogen, the fluid crystallizes into three distinct solid structures, namely, a low density plastic crystal, a hexagonal close-packed plastic crystal (with the same structure as ß-N2), and an A15 Frank-Kasper phase (cP8 structure corresponding to δ-N2). At the lower pressures studied the hexagonal close packed plastic crystal is the most stable phase, but at the higher pressures the stable phase is an orientationally ordered solid designated as CP1 that is never spontaneously formed in our crystallization simulations.

Nanocapillarity and Liquid Bridge-Mediated Force between Colloidal Nanoparticles.

In this work, we probe the concept of interface tension for ultrathin adsorbed liquid films on the nanoscale by studying the surface fluctuations of films down to the monolayer. Our results show that the spectrum of film height fluctuations of a liquid-vapor surface may be extended to ultrathin films provided we take into account the interactions of the substrate with the surface. Global fluctuations of the film height are described in terms of disjoining pressure, whereas surface deformations that are proportional to the interface area are accounted for by a film thickness-dependent surface tension. As a proof of concept, we model the capillary forces between colloidal nanoparticles held together by liquid bridges. Our results indicate that the classical equations for capillarity follow very precisely down to the nanoscale provided we account for the film height dependence of the surface tension.

Femtosecond laser reshaping yields gold nanorods with ultranarrow surface plasmon resonances.

The irradiation of gold nanorod colloids with a femtosecond laser can be tuned to induce controlled nanorod reshaping, yielding colloids with exceptionally narrow localized surface plasmon resonance bands. The process relies on a regime characterized by a gentle multishot reduction of the aspect ratio, whereas the rod shape and volume are barely affected. Successful reshaping can only occur within a narrow window of the heat dissipation rate: Low cooling rates lead to drastic morphological changes, and fast cooling has nearly no effect. Hence, a delicate balance must be achieved between irradiation fluence and surface density of the surfactant on the nanorods. This perfection process is appealing because it provides a simple, fast, reproducible, and scalable route toward gold nanorods with an optical response of exceptional quality, near the theoretical limit.

Premelting-Induced Smoothening of the Ice-Vapor Interface.

We perform computer simulations of the quasiliquid layer of ice formed at the ice-vapor interface close to the ice Ih-liquid-vapor triple point of water. Our study shows that the two distinct surfaces bounding the film behave at small wavelengths as atomically rough and independent ice-water and water-vapor interfaces. For long wavelengths, however, the two surfaces couple, large scale parallel fluctuations are inhibited, and the ice-vapor interface becomes smooth. Our results could help explain the complex morphology of ice crystallites.

Alimentos funcionales y protección de los consumidores. Régimen jurídico comunitario y español / No disponible

Los alimentos funcionales (AF) poseen efectos beneficiosos sobre funciones específicas del organismo humano, más allá de los efectos nutricionales habituales, y son efectivos para mejorar la salud y el bienestar de las personas o reducir el riesgo de enfermar. La presencia de los alimentos funcionales en el mercado exige garantías científicas acerca de su composición, fiabilidad y beneficios añadidos para la salud. Debe asegurarse un nivel elevado de protección de la vida y la salud de los consumidores de AF. La legislación alimentaria comunitaria general resulta plenamente aplicable a los AF, a falta de una normativa específica. En particular, resulta relevante la legislación sobre declaraciones nutricionales y de propiedades saludables en los alimentos. La legislación española debe respetar el rango jerárquico de la normativa de la UE en esta materia. Debe evitarse que el consumo de AF pueda llegar a generar adicción en las personas, ante la falsa creencia de que otro tipo de alimentos no son saludables o beneficiosos para el organismo. A tal efecto, el control, la condicionalidad y la regulación de la publicidad e información de los AF suministrada al consumidor resulta esencial (AU)

Functional foods (FF) have beneficial effects on specifi c functions of the human body, beyond the usual nutritional effects, and are effective in improving the health and welfare of people or reducing the risk of disease. The presence of FF on the market requires scientifi c guarantees regarding their composition, reliability and added health benefi ts. Authorities must ensure a high level of protection of the life and health of consumers of FF. General EU food law is fully applicable to FF in the absence of specifi c legislation. In particular, legislation on nutrition and health claims on foods is relevant. Spanish legislation must respect EU legislation in this area. Consumption of FF can potentially generate addiction in people, in the false belief that other foods are not healthy or benefi cial to the body. This danger must be avoided. Regulation on control and compliance of advertising and information provided to the consumer of FF is essential for this purpose (AU)