Nanogels and Microgels: From Model Colloids to Applications, Recent Developments, and Future Trends.

Nanogels and microgels are soft, deformable, and penetrable objects with an internal gel-like structure that is swollen by the dispersing solvent. Their softness and the potential to respond to external stimuli like temperature, pressure, pH, ionic strength, and different analytes make them interesting as soft model systems in fundamental research as well as for a broad range of applications, in particular in the field of biological applications. Recent tremendous developments in their synthesis open access to systems with complex architectures and compositions allowing for tailoring microgels with specific properties. At the same time state-of-the-art theoretical and simulation approaches offer deeper understanding of the behavior and structure of nano- and microgels under external influences and confinement at interfaces or at high volume fractions. Developments in the experimental analysis of nano- and microgels have become particularly important for structural investigations covering a broad range of length scales relevant to the internal structure, the overall size and shape, and interparticle interactions in concentrated samples. Here we provide an overview of the state-of-the-art, recent developments as well as emerging trends in the field of nano- and microgels. The following aspects build the focus of our discussion: tailoring (multi)functionality through synthesis; the role in biological and biomedical applications; the structure and properties as a model system, e.g., for densely packed arrangements in bulk and at interfaces; as well as the theory and computer simulation.

Locomotion of Ants Walking up Slippery Slopes of Granular Materials.

Many insects encounter locomotory difficulties in walking up sand inclines. This is masterfully exploited by some species for building traps from which prey are rarely able to escape, as the antlion and its deadly pit. The aim of this work is to tear apart the relative roles of granular material properties and slope steepness on the insect leg kinematics, gait patterns, and locomotory stability. For this, we used factorial manipulative experiments with different granular media inclines and the ant Aphaenogaster subterranea. Our results show that its locomotion is similar on granular and solid media, while for granular inclined slopes we observe a loss of stability followed by a gait pattern transition from tripod to metachronal. This implies that neither the discrete nature nor the roughness properties of sand alone are sufficient to explain the struggling of ants on sandy slopes: the interaction between sand properties and slope is key. We define an abnormality index that allows us to quantify the locomotory difficulties of insects walking up a granular incline. The probability of its occurrence reveals the local slipping of the granular media as a consequence of the pressure exerted by the ant's legs. Our findings can be extended to other models presenting locomotory difficulties for insects, such as slippery walls of urns of pitcher plants. How small arthropods walking on granular and brittle materials solve their unique stability trade-off will require a thorough understanding of the transfer of energy from leg to substrate at the particle level.

Sphere-Tubule Superstructures through Supramolecular and Supracolloidal Assembly Pathways.

While colloids have been widely employed as models for atoms and molecules, the current study proposes to extend their use as building blocks for supracolloidal frameworks. Hereby, the self-assembly between highly anisotropic supramolecular microtubules and soft spherical fluorescent microgels is explored using confocal laser scanning microscopy. The influence of the particle size and charge with respect to the catanionic tubule composition, which consists of two oppositely charged bile salt derivatives, is investigated. Under certain conditions, microgel particles are found to specifically interact with the extremities of the tubular aggregates and hierarchically self-assemble into various superstructures varying from virus-like assemblies to supracolloidal networks. The reported approach is envisioned to open new self-assembly routes toward ordered hybrid superstructures where the spherical colloids act as responsive linkers of tubular structures.

An instrument for studying granular media in low-gravity environment.

A new experimental facility has been designed and constructed to study driven granular media in a low-gravity environment. This versatile instrument, fully automatized, with a modular design based on several interchangeable experimental cells, allows us to investigate research topics ranging from dilute to dense regimes of granular media such as granular gas, segregation, convection, sound propagation, jamming, and rheology-all without the disturbance by gravitational stresses active on Earth. Here, we present the main parameters, protocols, and performance characteristics of the instrument. The current scientific objectives are then briefly described and, as a proof of concept, some first selected results obtained in low gravity during parabolic flight campaigns are presented.

Improved slow magnetic relaxation in optically pure helicene-based DyIII single molecule magnets.

Racemic and optically pure [Dy(hfac)3(L)] complexes with L = 3-(2-pyridyl)-4-aza[6]-helicene have been synthesized and characterized. Both the racemic and enantiopure forms behave as single molecule magnets in their crystalline phase, while electronic circular dichroism activity is evidenced. Ab initio calculations on isolated complexes followed by the determination of intermolecular dipolar couplings allowed the rationalization of the different low-temperature magnetic behaviours. The enantiopure SMM differs from the racemic one by the presence of a hysteresis loop in the former system.

Experimental velocity fields and forces for a cylinder penetrating into a granular medium.

We present here a detailed granular flow characterization together with force measurements for the quasi-bidimensional situation of a horizontal cylinder penetrating vertically at a constant velocity in dry granular matter between two parallel glass walls. In the velocity range studied here, the drag force on the cylinder does not depend on the velocity V(0) and is mainly proportional to the cylinder diameter d. While the force on the cylinder increases with its penetration depth, the granular velocity profile around the cylinder is found to be stationary with fluctuations around a mean value leading to the granular temperature profile. Both mean velocity profile and temperature profile exhibit strong localization near the cylinder. The mean flow perturbation induced by the cylinder decreases exponentially away from the cylinder on a characteristic length λ that is mainly governed by the cylinder diameter for a large enough cylinder/grain size ratio d/d(g): λ~d/4+2d(g). The granular temperature exhibits a constant plateau value T(0) in a thin layer close to the cylinder of extension δ(T(0))~λ/2 and decays exponentially far away with a characteristic length λ(T) of a few grain diameters (λ(T)~3d(g)). The granular temperature plateau T(0) that scales as V(0)(2)d(g)/d is created by the flow itself from the balance between the "granular heat" production by the shear rate V(0)/λ over δ(T(0)) close to the cylinder and the granular dissipation far away.

Dense granular flow around a penetrating object: experiment and hydrodynamic model.

We present in this Letter experimental results on the bidimensional flow field around a cylinder penetrating into dense granular matter, together with drag force measurements. A hydrodynamic model based on extended kinetic theory for dense granular flow reproduces well the flow localization close to the cylinder and the corresponding scalings of the drag force, which is found to not depend on velocity, but linearly on the pressure and on the cylinder diameter and weakly on the grain size. Such a regime is found to be valid at a low enough "granular" Reynolds number.

Investigating acoustic-induced deformations in a foam using multiple light scattering.

We have studied the effect of an external acoustic wave on bubble displacements inside an aqueous foam. The signature of the acoustic-induced bubble displacements is found using a multiple light scattering technique, and occurs as a modulation on the photon correlation curve. Measurements for various sound frequencies and amplitudes are compared to analytical predictions and numerical simulations. These comparisons finally allow us to elucidate the nontrivial acoustic displacement profile inside the foam; in particular, we find that the acoustic wave creates a localized shear in the vicinity of the solid walls holding the foam, as a consequence of inertial contributions. This study of how bubbles "dance" inside a foam as a response to sound turns out to provide new insights on foam acoustics and sound transmission into a foam, foam deformation at high frequencies, and analysis of light scattering data in samples undergoing nonhomogeneous deformations.

Granular medium impacted by a projectile: experiment and model.

We present a minimal discrete model for the propagation of energy through a 3D granular medium impacted by a particulate projectile. In this model, energy is transferred from grain to grain via binary collision events. This description can be successfully applied to the analysis of the collision process of a single spherical particle (of diameter donto a half space of granular medium composed of similarly sized particles. The model reproduces remarkably well the experimental observations. Besides, the present model provides a clear picture of the mechanism of energy propagation. A continuum version of the model, where the energy propagation from bead to bead is characterized by a diffusion equation, is derived. The diffusion coefficient is found to be proportional to the ratio of d(2) to the characteristic collision time Tau(c) . The numerical value of the coefficient of proportionality is essentially governed by the geometry of the packing. This paper constitutes an extension of a previously published letter (J. Crassous, D. Beladjine, A. Valance, Phys. Rev. Lett. 99, 248001 (2007)).

Multispeckle diffusing wave spectroscopy of colloidal particles suspended in a random packing of glass spheres.

We use a multispeckle diffusing wave spectroscopy (MSDWS) method to study the ensemble-averaged dynamics of the fluctuating speckle pattern when illuminating colloidal particles suspended in a static and opaque porous medium with a coherent light source. Experiments were performed with Brownian latex particles in a random packing of glass spheres. The mixing of the light scattered by the moving colloidal particles and the porous matrix gives rise to a plateau value of the intensity autocorrelation function in the long-waiting-time limit. From the plateau in the correlation function, we can determine the fraction of light scattered from moving particles and estimate the photon mean free path in the colloidal solution. The method opens up promising possibilities to probe the static fraction in semisolid materials.

Quantitative analysis of polymer colloids by cryo-transmission electron microscopy.

The structure of colloidal latex particles in dilute suspension at room temperature is investigated by cryogenic transmission electron microscopy (cryo-TEM). Two types of particles are analyzed: (i) core particles made of polystyrene with a thin layer of poly(N-isopropylacrylamide) (PNIPAM) and (ii) core-shell particles consisting of core particles onto which a network of cross-linked PNIPAM is affixed. Both systems are also studied by small-angle X-ray scattering (SAXS). The radial density profile of both types of particles have been derived from the cryo-TEM micrographs by image processing and compared to the results obtained by SAXS. Full agreement is found for the core particles. There is a discrepancy between the two methods in case of the core-shell particles. The discrepancy is due to the buckling of the network affixed to the surface. The buckling is clearly visible in the cryo-TEM pictures. The overall dimensions derived from cryo-TEM agree well with the hydrodynamic radius of the particles. The comparison of these data with the analysis by SAXS shows that SAXS is only sensitive to the average radial structure as expected. All data show that cryo-TEM micrographs can be evaluated to yield quantitative information about the structure of colloidal particles.

Rheology of confined granular flows: scale invariance, glass transition, and friction weakening.

We study fully developed, steady granular flows confined between parallel flat frictional sidewalls using numerical simulations and experiments. Above a critical rate, sidewall friction stabilizes the underlying heap at an inclination larger than the angle of repose. The shear rate is constant and independent of inclination over much of the flowing layer. In the direction normal to the free surface, the solid volume fraction increases on a scale equal to half the flowing layer depth. Beneath a critical depth at which internal friction is invariant, grains exhibit creeping and intermittent cage motion similar to that in glasses, causing gradual weakening of friction at the walls.

Shear stresses of colloidal dispersions at the glass transition in equilibrium and in flow.

We consider a model dense colloidal dispersion at the glass transition, and investigate the connection between equilibrium stress fluctuations, seen in linear shear moduli, and the shear stresses under strong flow conditions far from equilibrium, viz., flow curves for finite shear rates. To this purpose, thermosensitive core-shell particles consisting of a polystyrene core and a cross-linked poly(N-isopropylacrylamide) shell were synthesized. Data over an extended range in shear rates and frequencies are compared to theoretical results from integrations through transients and mode coupling approaches. The connection between nonlinear rheology and glass transition is clarified. While the theoretical models semiquantitatively fit the data taken in fluid states and the predominant elastic response of glass, a yet unaccounted dissipative mechanism is identified in glassy states.

Diffusive wave spectroscopy of a random close packing of spheres.

We are interested in the propagation of light in a random packing of dielectric spheres within the geometrical optics approximation. Numerical simulations are performed using a ray tracing algorithm. The effective refractive indexes and the transport mean free path are computed for different refractive indexes of spheres and intersticial media. The variations of the optical path length under small deformations of the spheres assembly are also computed and compared to the results of Diffusive Wave Spectroscopy experiments. Finally, we propose a measure of the transport mean free path and a Diffusive Wave Spectroscopy experiment on a packing of glass spheres. The results of those experiments agree with the predictions of this ray tracing approach.

Thermosensitive core-shell particles as model systems for studying the flow behavior of concentrated colloidal dispersions.

We report on a comprehensive investigation of the flow behavior of colloidal thermosensitive core-shell particles at high densities. The particles consist of a solid core of poly(styrene) onto which a network of cross-linked poly(N-isopropylacrylamide) is affixed. Immersed in water the shell of these particles will swell if the temperature is low. Raising the temperature above 32 degrees C leads to a volume transition within this shell which leads to a marked shrinking of the shell. The particles have well-defined core-shell structure and a narrow size distribution. The remaining electrostatic interactions due to a small number of charges affixed to the core particles can be screened by adding 0.05M KCl to the suspensions. Below the lower critical solution temperature at 32 degrees C the particles are purely repulsive. Above this transition, a thermoreversible coagulation takes place. Lowering the temperature again leads to full dissociation of the aggregates formed by this process. The particles crystallize for effective volume fractions between 0.48 and 0.55. The crystallites can be molten by shear in order to reach a fluid sample again. The reduced shear stress measured in this metastable disordered state was found to be a unique function of the shear rate and the effective volume fraction. These reduced flow curves thus obtained can be described quantitatively by the theory of Fuchs and Cates [Phys. Rev. Lett. 89, 248304 (2002)] which is based on the mode-coupling theory of the glass transition.

The chiral molecule CHClFI: first determination of its molecular parameters by Fourier transform microwave and millimeter-wave spectroscopies supplemented by ab initio calculations.

The rotational spectrum of chlorofluoroiodomethane (CHClFI) has been investigated. Because its rotational spectrum is extremely crowded, extensive ab initio calculations were first performed in order to predict the molecular parameters. The low J transitions were measured using a pulsed-molecular-beam Fourier transform spectrometer, and the millimeter-wave spectrum was measured to determine accurate centrifugal distortion constants. Because of the high resolution of the experimental techniques, the analysis yielded accurate rotational constants, centrifugal distortion corrections, and the complete quadrupole coupling tensors for the iodine and chlorine nuclei, as well as the contribution of iodine to the spin-rotation interaction. These molecular parameters were determined for the two isotopologs CH35ClFI and CH37ClFI. They reproduce the observed transitions within the experimental accuracy. Moreover, the ab initio calculations have provided a precise equilibrium molecular structure. Furthermore, the ab initio molecular parameters are found in good agreement with the corresponding experimental values.

Rheological properties of a highly confined film of a lyotropic lamellar phase.

We investigated the rheological properties of a thin film of a lyotropic lamellar phase with a Dynamic Surface Forces Apparatus. The minimum thickness of the film is varied between one to several tens of layers by confining the materials between solid surfaces. The rheometric properties are measured with the application of a small harmonic compression. These properties depend clearly on the smectic order of the material. Whole mechanical properties may be easily described by taking into account interactions between membranes and motion of the dislocation line loops. In particular, it is shown that at the dynamical frequencies investigated in this study, the solvent flows between membranes which remain undeformed. Consequences and perspectives of this study will be discussed.

Adhesion between weakly rough beads.

Cohesion effects are of prime importance in powders and granular media, and they are strongly affected by the roughness of the grain surface. We report measurements of the adhesion force between surfaces of Pyrex having a nanometric roughness, with a surface force apparatus. The two surfaces are immersed in liquid n-dodecane. The adhesion force measured is much smaller than expected in the case of smooth surfaces. We find that the adhesion force depends on the maximal load that has been applied on the surfaces, but does not depend on the time during which they have been in contact. We propose a model of plastic deformation of the small asperities in a macroscopic Hertz contact which is in good agreement with the experimental data.

Nanorheology: An investigation of the boundary condition at hydrophobic and hydrophilic interfaces.

It has been shown that the flow of a simple liquid over a solid surface can violate the so-called no-slip boundary condition. We investigate the flow of polar liquids, water and glycerol, on a hydrophilic Pyrex surface and a hydrophobic surface made of a Self-Assembled Monolayer of OTS (octadecyltrichlorosilane) on Pyrex. We use a Dynamic Surface Force Apparatus (DSFA) which allows one to study the flow of a liquid film confined between two surfaces with a nanometer resolution. No-slip boundary conditions are found for both fluids on hydrophilic surfaces only. Significant slip is found on the hydrophobic surfaces, with a typical length of one hundred nanometers.

The bromochlorofluoromethane saga.

Synthesis of optically active samples of bromochlorofluoromethane (CHFClBr) was performed via fractional crystallisation of the strychnine salts of bromochlorofluoroacetic acid (FClBrCCO2H). The S-(+) (R-(-)) absolute configuration of the acid was established by X-ray crystallography and the S-(+) (R-(-)) absolute configuration of the haloform was determined using Raman Optical Activity (ROA) and molecular modelling of the enantioselective molecular recognition process of CHFClBr by the chiral cryptophane-C. From these stereochemical assignments it was observed that the decarboxylation used to obtain S-(+)- and R-(-)-CHFClBr from respectively S-(+)- and R-(-)-FClBrCCO2H occurred with retention of configuration. Finally, the first parity violation (PV) test on CHFClBr was performed and yielded an upper bound for this small stereophysical effect.