Shortcomings of the Bond Orientational Order Parameters for the Analysis of Disordered Particulate Matter

Local structure characterization with the bond-orientational order parameters q4, q6, ... introduced by Steinhardt et al. has become a standard tool in condensed matter physics, with applications including glass, jamming, melting or crystallization transitions and cluster formation. Here we discuss two fundamental flaws in the definition of these parameters that significantly affect their interpretation for studies of disordered systems, and offer a remedy. First, the definition of the bond-orientational order parameters considers the geometrical arrangement of a set of neighboring spheres NN(p) around a given central particle p; we show that procedure to select the spheres constituting the neighborhood NN(p) can have greater influence on both the numerical values and qualitative trend of ql than a change of the physical parameters, such as packing fraction. Second, the discrete nature of neighborhood implies that NN(p) is not a continuous function of the particle coordinates; this discontinuity, inherited by ql, leads to a lack of robustness of the ql as structure metrics. Both issues can be avoided by a morphometric approach leading to the robust Minkowski structure metrics ql'. These ql' are of a similar mathematical form as the conventional bond-orientational order parameters and are mathematically equivalent to the recently introduced Minkowski tensors [Europhys. Lett. 90, 34001 (2010); Phys. Rev. E. 85, 030301 (2012)]

Jammed Spheres: Minkowski Tensors Reveal Onset of Local Crystallinity

The local structure of disordered jammed packings of monodisperse spheres without friction, generated by the Lubachevsky-Stillinger algorithm, is studied for packing fractions above and below 64%. The structural similarity of the particle environments to fcc or hcp crystalline packings (local crystallinity) is quantified by order metrics based on rank-four Minkowski tensors. We find a critical packing fraction \phi_c \approx 0.649, distinctly higher than previously reported values for the contested random close packing limit. At \phi_c, the probability of finding local crystalline configurations first becomes finite and, for larger packing fractions, increases by several orders of magnitude. This provides quantitative evidence of an abrupt onset of local crystallinity at \phi_c. We demonstrate that the identification of local crystallinity by the frequently used local bond-orientational order metric q_6 produces false positives, and thus conceals the abrupt onset of local crystallinity. Since the critical packing fraction is significantly above results from mean-field analysis of the mechanical contacts for frictionless spheres, it is suggested that dynamic arrest due to isostaticity and the alleged geometric phase transition in the Edwards framework may be disconnected phenomena

Antiinflammatory Therapy with Canakinumab for Atherosclerotic Disease

Background: Experimental and clinical data suggest that reducing inflammation without affecting lipid levels may reduce the risk of cardiovascular disease. Yet, the inflammatory hypothesis of atherothrombosis has remained unproved. Methods: We conducted a randomized, double-blind trial of canakinumab, a therapeutic monoclonal antibody targeting interleukin-1β, involving 10,061 patients with previous myocardial infarction and a high-sensitivity C-reactive protein level of 2 mg or more per liter. The trial compared three doses of canakinumab (50 mg, 150 mg, and 300 mg, administered subcutaneously every 3 months) with placebo. The primary efficacy end point was nonfatal myocardial infarction, nonfatal stroke, or cardiovascular death. RESULTS: At 48 months, the median reduction from baseline in the high-sensitivity C-reactive protein level was 26 percentage points greater in the group that received the 50-mg dose of canakinumab, 37 percentage points greater in the 150-mg group, and 41 percentage points greater in the 300-mg group than in the placebo group. Canakinumab did not reduce lipid levels from baseline. At a median follow-up of 3.7 years, the incidence rate for the primary end point was 4.50 events per 100 person-years in the placebo group, 4.11 events per 100 person-years in the 50-mg group, 3.86 events per 100 person-years in the 150-mg group, and 3.90 events per 100 person-years in the 300-mg group. The hazard ratios as compared with placebo were as follows: in the 50-mg group, 0.93 (95% confidence interval [CI], 0.80 to 1.07; P = 0.30); in the 150-mg group, 0.85 (95% CI, 0.74 to 0.98; P = 0.021); and in the 300-mg group, 0.86 (95% CI, 0.75 to 0.99; P = 0.031). The 150-mg dose, but not the other doses, met the prespecified multiplicity-adjusted threshold for statistical significance for the primary end point and the secondary end point that additionally included hospitalization for unstable angina that led to urgent revascularization (hazard ratio vs. placebo, 0.83; 95% CI, 0.73 to 0.95; P = 0.005). Canakinumab was associated with a higher incidence of fatal infection than was placebo. There was no significant difference in all-cause mortality (hazard ratio for all canakinumab doses vs. placebo, 0.94; 95% CI, 0.83 to 1.06; P = 0.31). Conclusions: Antiinflammatory therapy targeting the interleukin-1β innate immunity pathway with canakinumab at a dose of 150 mg every 3 months led to a significantly lower rate of recurrent cardiovascular events than placebo, independent of lipid-level lowering. (Funded by Novartis; CANTOS ClinicalTrials.gov number, NCT01327846.

Effet géométriques dans les transitions de mouillage et dans la physique des empilements désordonnés

This thesis is devoted to several aspects of geometry and morphology in wetting problems and hard sphere packings. First, we propose a new method to simulate wetting and slip on nanostructured substrates: a phase field model associated with a dynamical density theory approach. We showed omniphobicity, meaning repellency, no matter the chemical properties of the liquid on monovalued surfaces, i.e. surfaces without overhangs, which is in contradiction with the macroscopic Cassie-Baxter-Wenzel theory, can produce so-called We checked systematically the impact of the surface parameters on omniphobic repellency, and we show that the key ingredient are line tensions, which emerge from needle shaped surface structures. Geometrical effects have also an important influence on glassy or jammed systems, for example amorphous hard sphere systems in infinite pressure limit. Such hard sphere packings got stuck in a so-called jammed phase, and we shall demonstrate that the local structure in such systems is universal, i.e. independent of the protocol of the generation. For this, robust order parameters - so-called Minkowski tensors - are developed, which overcome robustness deficiencies of widely used order parameters. This leads to a unifying picture of local order parameters, based on geometrical principles. Furthermore, we find with the Minkowski tensor analysis crystallization in jammed sphere packs at the random closed packing pointCette thèse porte sur différents aspects géométriques et morphologiques concernant des problèmes de mouillage et d'empilement de sphères. Nous proposons tout d'abord une nouvelle méthode de simulation pour étudier le mouillage et le glissement d'un liquide sur une surface nanostructurée: un modèle de champ de phase en lien avec la théorie de la fonctionnelle de la densité dynamique. Nous étudions grâce à cette méthode la possibilité de transformer une surface quelconque en surface omniphobe (c'est à dire qui repousse tous les liquides). Nous montrons que contrairement à la théorie classique de Cassie-Baxter-Wenzel, il est possible d'inverser la mouillabilité d'une surface en la texturant, et nous montrons qu'une surface monovaluée, i.e. sans constrictions, peut produire un comportement omniphobe c'est à dire repousser tous les liquides grâce à un effet de pointe. La géométrie a également un effet considérable dans les milieux vitreux ou bloqués. Les empilements aléatoires de sphères conduisent par exemple à des état bloqués ("jamming") et nous montrons que la structure locale de ces systèmes est universelle, c'est à dire indépendante de la méthode de préparation. Pour cela, nous introduisons des paramètres d'ordre - les tenseurs de Minkowski - qui suppriment les problèmes de robustesse qu'ont les paramètres d'ordre utilisés classiquement. Ces nouveaux paramètres d'ordre conduisent à une vision unifiée, basée sur des principes géométriques. Enfin, nous montrons grâce aux tenseurs de Minkowski que les empilements de sphères se mettent à cristalliser au delà du point d'empilement aléatoire le plus dense ("random close packing"

Geometrisch bestimmte Phasen bei der Benetzung von nanostrukturierten Oberflächen und bei Jamming

This thesis is devoted to several aspects of geometry and morphology in wetting problems and hard sphere packings. First, we propose a new method to simulate wetting and slip on nanostructured substrates: a phase field model associated with a dynamical density theory approach. We showed omniphobicity, meaning repellency, no matter the chemical properties of the liquid on monovalued surfaces, i.e.~surfaces without overhangs, which is in contradiction with the macroscopic Cassie-Baxter-Wenzel theory , can produce so-called We checked systematically the impact of the surface parameters on omniphobic repellency, and we show that the key ingredient are line tensions, which emerge from needle shaped surface structures. Geometrical effects have also an important influence on glassy or jammed systems, for example amorphous hard sphere systems in infinite pressure limit. Such hard sphere packings got stuck in a so-called jammed phase, and we shall demonstrate that the local structure in such systems is universal, i.e.~independent of the protocol of the generation. For this, robust order parameters---so-called Minkowski tensors-are developed, which overcome robustness deficiencies of widely used order parameters. This leads to a unifying picture of local order parameters, based on geometrical principles. Furthermore, we find with the Minkowski tensor analysis crystallization in jammed sphere packs at the random closed packing point.Cette thèse porte sur différents aspects géométriques et morphologiques concernant des problèmes de mouillage et d'empilement de sphères. Nous proposons tout d'abord une nouvelle méthode de simulation pour étudier le mouillage et le glissement d'un liquide sur une surface nanostructurée: un modèle de champ de phase en lien avec la théorie de la fonctionnelle de la densité dynamique. Nous étudions grâce à cette méthode la possibilité de transformer une surface quelconque en surface omniphobe (c'est à dire qui repousse tous les liquides). Nous montrons que contrairement à la théorie classique de Cassie-Baxter-Wenzel, il est possible d'inverser la mouillabilité d'une surface en la texturant, et nous montrons qu'une surface monovaluée, i.e. sans constrictions, peut produire un comportement omniphobe c'est à dire repousser tous les liquides grâce à un effet de pointe. La géométrie a également un effet considérable dans les milieux vitreux ou bloqués. Les empilements aléatoires de sphères conduisent par exemple à des état bloqués ("jamming") et nous montrons que la structure locale de ces systèmes est universelle, c'est à dire indépendante de la méthode de préparation. Pour cela, nous introduisons des paramètres d'ordre - les tenseurs de Minkowski - qui suppriment les problèmes de robustesse qu'ont les paramètres d'ordre utilisés classiquement. Ces nouveaux paramètres d'ordre conduisent à une vision unifiée, basée sur des principes géométriques. Enfin, nous montrons grâce aux tenseurs de Minkowski que les empilements de sphères se mettent à cristalliser au delà du point d'empilement aléatoire le plus dense ("random close packing"

Transport, phase transitions, and wetting in micro/nanochannels: A phase field/DDFT approach

While the flow of a liquid in a macroscopic channel is usually described using hydrodynamics with no-slip boundary conditions at the walls of the channel, transport phenomena in microchannels involve physics at many different scales due to the interplay between the micrometric section of the channel and the micro- or nanometric roughness of the boundaries. Roughness can have many different effects such as increasing the friction between the liquid and the walls (leading to the macroscopic no-slip boundary condition) or on the contrary reduce it thanks to the Wenzel–Cassie–Baxter wetting transition induced by capillarity. Here we detail a phase-field/dynamic density functional theory model able to account for the wetting transitions, the resulting friction between the wall and the fluid, and compressible hydrodynamics at high viscosity contrast

A Bicontinuous Mesophase Geometry with Hexagonal Symmetry

We report that a specific realization of Schwarz's triply periodic hexagonal minimal surface is isotropic with respect to the Doi-Ohta interface tensor and simultaneously has minimal packing and stretching frustration similar to those of the commonly found cubic bicontinuous mesophases. This hexagonal surface, of symmetry P63/mmc with a lattice ratio of c/a = 0.832, is therefore a likely candidate geometry for self-assembled lipid/surfactant or copolymer mesophases. Furthermore, both the peak position ratios in its powder diffraction pattern and the elastic moduli closely resemble those of the cubic bicontinuous phases. We therefore argue that a genuine possibility of experimental misidentification exists

MOESM1 of Intracellular product recycling in high succinic acid producing yeast at low pH

Additional file 1. Supplementary information