arXiv subjects

Ghazi Ben Messaoud

Publications and source records attributed to Ghazi Ben Messaoud.

5 recordsLinked to original sources

arXiv2026

Unmasking the internal structure of casein micelles through enzymatic hydrolysis: A SAXS study

Casein micelles, one of the most studied natural association colloids, are supramolecular assemblies of caseins and colloidal calcium phosphate that constitute the fundamental building blocks of dairy matrices. Despite extensive investigation, the internal structure of casein micelles remains debated. While $κ$-casein is known to ensure colloidal stability of casein micelle suspension, the spatial organization of casein fractions and salts is still unresolved, and several structural models coexist. Small-angle scattering is a method of choice to probe biological colloids \emph{in situ}, yet interpretation of scattering data remains challenging due to the hierarchical nature of casein micelles. Here we address this issue by probing micelle structure during enzymatic gelation induced by chymosin, which cleaves $κ$-casein and triggers aggregation. Using time-resolved SAXS, we probe structural changes throughout the sol-gel transition over length scales from 3 nm to 3 $μ$m. First, we show that enzyme-driven aggregation, counterintuitively, reveals information about the internal organization of casein micelles: the reduction of specific surface area during gelation unmasks a high-q structural peak previously observed under contrast-matching conditions. Second, we report that $κ$-casein cleavage leads to a gradual disappearance of the structural feature at intermediate scales. Analysis of the disappearance kinetics and comparison to structural models reveal that $κ$-casein cleavage induces a progressive relaxation of the colloidal porous substructure, providing direct evidence for its contribution to micellar organization. More broadly, these results demonstrate that the gelation process provides unique access to the internal structure of biological colloids and offers new perspectives for interpreting scattering data in complex soft-matter systems.

cond-mat.soft↗

arXiv2021

pH Switchable Pickering Emulsions Stabilized by Polyelectrolyte Biosurfactant Complex Coacervate Colloids

Polyelectrolyte-surfactant complexes (PESCs) have long been employed as oil-in-water (o/w) emulsions stabilizers, but never in the structure of colloidal complex coacervates providing a Pickering effect. The complexed state of PESCs could make them unsuitable o/w Pickering emulsifiers, which instead require a balance between colloidal structure and stability, amphiphilicity and wettability. Here we hypothesize that PESCs coacervates are efficient Pickering stabilizers. Instead of classical surfactants, we employ sophorolipid (SL) biosurfactants, atypical anionic/neutral stimuli-responsive biosurfactants. Despite their tunable charge and mild amphiphilic character, they can be used in combination with cationic/neutral polyelectrolytes (chitosan, CHL, or poly-L-lysine, PLL) to form PESC coacervates for the development of biobased, but also pH-switchable, Pickering emulsions.Aqueous solutions of SL-CHL (or SL-PLL) complex coacervates are emulsified with dodecane. Confocal laser scanning microscopy (CLSM) and scanning electron microscopy under cryogenic conditions (cryo-SEM) demonstrate the Pickering effect, while optical microscopy and oscillatory rheology respectively assess the emulsion formation and relative viscoelastic properties.Both SL-CHL and SL-PLL PESCs stabilize o/w emulsions up to $Φ$oil of 0.7 only in the pH region of complex coacervation (6 < pH < 9): outside this range, phase separation occurs. Rheology shows a typical solid-like response and mechanical recovery upon applying large deformations. CLSM and cryo-SEM highlight a colloidal structure, associated to the complex coacervates, of the oil/water interface and suggest a Pickering effect. These findings demonstrate the Pickering effect from PESC coacervates and the possibility to use biobased and biocompatible components, with application potential in cosmetics, food science, or oil recovery.

cond-mat.soft↗

arXiv2021

Palmitic Acid Sophorolipid Biosurfactant: From Self-Assembled Fibrillar Network (SAFiN) To Hydrogels with Fast Recovery

Nanofibers are an interesting phase into which amphiphilic molecules can self-assemble. Described for a large number of synthetic lipids, they were seldom reported for natural lipids like microbial amphiphiles, known as biosurfactants. In this work, we show that the palmitic acid congener of sophorolipids (SLC16:0), one of the most studied families of biosurfactants, spontaneously forms a self-assembled fiber network (SAFiN) at pH below 6 through a pH jump process. pH-resolved in-situ Small Angle X-ray Scattering (SAXS) shows a continuous micelle-to-fiber transition, characterized by an enhanced core-shell contrast between pH 9 and pH 7 and micellar fusion into flat membrane between pH 7 and pH 6, approximately. Below pH 6, homogeneous, infinitely long nanofibers form by peeling off the membranes. Eventually, the nanofiber network spontaneously forms a thixotropic hydrogel with fast recovery rates after applying an oscillatory strain amplitude out of the linear viscoelastic regime (LVER): after being submitted to strain amplitudes during 5 min, the hydrogel recovers about 80% and 100% of its initial elastic modulus after, respectively, 20 s and 10 min. Finally, the strength of the hydrogel depends on the medium's final pH, with an elastic modulus fivefold higher at pH 3 than at pH 6.

cond-mat.soft↗

arXiv2020

Single-Molecule Lamellar Hydrogels from Bolaform Microbial Glucolipids

Lipid lamellar hydrogels are rare soft fluids composed of a phospholipid lamellar phase instead of fibrillar networks. The mechanical properties of these materials are controlled by defects, induced by local accumulation of a polymer or surfactant in a classical lipid bilayer. Herein we report a new class of lipid lamellar hydrogels composed of one single bolaform glycosylated lipid obtained by fermentation. The lipid is self-organized into flat interdigitated membranes, stabilized by electrostatic repulsive forces and stacked in micrometer-sized lamellar domains. The defects in the membranes and the interconnection of the lamellar domains are responsible, from the nano- to the micrometer scales, for the elastic properties of the hydrogels. The lamellar structure is probed by combining small angle x-ray and neutron scattering (SAXS, SANS), the defect-rich lamellar domains are visualized by polarized light microscopy while the elastic properties are studied by oscillatory rheology. The latter show that both storage G' and loss G'' moduli scale as a weak power-law of the frequency, that can be fitted with fractional rheology models. The hydrogels possess rheo-thinning properties with second-scale recovery. We also show that ionic strength is not only necessary, as one could expect, to control the interactions in the lamellar phase but, most importantly, it directly controls the elastic properties of the lamellar gels.

cond-mat.soft↗

arXiv2019

Soft lamellar solid foams from ice-templating of self-assembled lipid hydrogels: organization drives the mechanical properties

Ice-templating, also referred to as freeze-casting, is a process exploiting unidirectional crystallization of ice to structure macroporous materials from colloidal solutions. Commonly applied to inorganic and polymeric materials, we employ it here to cast soft self-assembled matter into spongy solid foams. Use of ice-templating to cast soft matter is generally confined to polymers. In the case of polymeric hydrogels, cross-linking ensures a good stability towards the harsh conditions (fast cooling at temperatures as low as-80{\textdegree}C) employed during ice-templating. However, freeze-casting of soft systems held together by weak interactions, like in physical gels, has not been explored, because the nonequilibrium conditions could easily disrupt the nano and macroscale organization of self-assembled matter, resulting in a cruel loss of mechanical properties. Whether this is a general assumption or a more specific relationship exists between the structure of the physical gel and the properties of the macroporous solid after ice-templating is the question addressed in this work. We compare two self-assembled lipid hydrogels, of analogous chemical composition and comparable elastic properties under ambient conditions, but different structure: isotropic entangled self-assembled fibers against heterogeneous lipid lamellar phase. Our results show that both materials possess the same phase (fibrillar and lamellar) before 2 and after freeze-casting but the mechanical properties are absolutely at the opposite: the fibrillar hydrogel provides a brittle, highly anisotropic, macroporous fibrous solid while the lamellar hydrogel provides soft, spongy, solid foam with isotropic Young moduli of several kPa, in the same order of magnitude as some soft living tissues.

cond-mat.soft↗