Well-defined double hydrophilic block copolymers (DHBCs) of poly(ethylene glycol)-block-poly(N,N-diethyla-crylamide) (PEG-b-PDEAm) were synthesized via a reversible addition-fragmentation chain-transfer (RAFT) polymerization of N,N-diethylacrylamide (DEAm) using dithioester terminated PEG of different chain lengths as macro-chain transfer agents. Controlled molecular weight and narrow molecular weight distribution were achieved as proven by size exclusion chromatography (SEC). Cloud points (CP) were determined via turbidity measurements with ultraviolet-visible spectroscopy (UV-vis) and LCST by differential scanning micro-calori-metry (micro-DSC). They range from 32 to 40°C depending on the PDEAm length block and its concentration. Above the LCST, fluorescence spectroscopy and dynamic light scattering (DLS) demonstrated that the PEG-b-PDEAm copolymers self-organized into large aggregates. More interestingly, copolymers pre-aggregated at relatively high concentrations below the LCST.

Wheat gluten, one of the most complex viscoelastic protein networks in nature, is unique to get the specific texture of bread. Due to its complex protein composition, its insolubility in most solvents and the very high molar mass of half of the proteins (glutenin, the other half being gliadin), the architecture of the network is still not well understood. In this work, we have investigated model gluten protein extracts with contrasted compositions in glutenin and gliadin solubilized in a mild chaotropic solvent: ethanol/water (50/50 v/v). The samples display a liquid-liquid phase separation with an upper critical solution temperature that depends on the protein composition. The phase diagrams are consistent with the presence of supramolecular assemblies of proteins. To confirm the presence of these assemblies and fully characterize the objects dispersed in ethanol/water, we have used an asymmetrical flow field-flow fractionation (AsFlFFF) setup coupled with differential refractive index, multi-angle light scattering and dynamic light scattering detections to probe very dilute protein suspensions. We have identified three classes of objects, with distinctive molar mass, characteristic size and conformation: protein monomers, polymeric structures, and very loose protein assemblies with molar mass larger than 2.10 6 g/mol. A molecular characterization of the species by size exclusion chromatography in a denaturing solvent shows that polymers and assemblies are mainly composed of glutenin and ω-gliadin. The high content of ω-gliadin, devoid of cysteines, indicates the importance of non-covalent interactions involved in protein assemblies and might play a major role in gluten rheology

Free solution capillary-electrophoresis (CE) is a powerful separation technique for the characterization of diblock copolymers. In this work, four series of double-hydrophilic anionic and cationic block copolymers, namely, poly(acrylamide)-block-poly(acrylic acid) (PAM-b-PAA), poly(acrylamide)-block-poly((3-acrylamidopropyl)trimethylammonium chloride) (PAM-b-PAPTAC), poly(ethylene oxide)-block-poly(acrylic acid) (PEO-b-PAA) and poly(poly(ethylene glycol) methyl ether acrylate)-block-poly(acrylic acid) (P(PEGA)-b-PAA), were synthesized by reversible additionfragmentation chain transfer (RAFT) polymerization and characterized by CE. The electrophoretic mobility distributions of the copolymers were transformed into distributions of composition ratio by introducing a retardation parameter, Xexp,, that represents the hydrodynamic drag retardation due to the neutral block of the copolymer. A linear correlation between Xexp and the ratio of the degrees of polymerization of each blocks was experimentally established and was consistent with the model of electrophoretic mobility of composite macromolecules with hydrodynamic coupling. Finally, the comparison of the distributions between the different copolymer families was significantly improved by considering the distributions in composition ratio compared to the electrophoretic mobility distributions, since it takes into account the differences in solvation, expansion and drag force according to the chemical nature of the blocks.

The mechanical properties of soft matter are of great importance in countless applications, in addition of being an active field of academic research. Given the relative ease with which soft materials can be deformed, their non-linear behavior is of particular relevance. Large loads eventually result in material failure. In this Perspective article, we discuss recent work aiming at detecting precursors of failure by scrutinizing the microscopic structure and dynamics of soft systems under various conditions of loading. In particular, we show that the microscopic dynamics is a powerful indicator of the ultimate fate of soft materials, capable of unveiling precursors of failure up to thousands of seconds before any macroscopic sign of weakening.

We report the measurement of the interaction energy between a charged Brownian polystyrene particle and an air–water interface. The interaction potential is obtained from the Boltzmann equation by tracking particle interface distance with a specifically designed Dual-Wave Reflection Interference Microscopy (DW-RIM) setup. The particle has two equilibrium positions located at few hundreds of nanometers from the interface. The farthest position is well accounted by a DLVO model complemented by gravity. The closest one, not predicted by current models, more frequently appears in water solutions at relatively high ions concentrations, when electrostatic interaction is screened out. It is accompanied by a frozen rotational diffusion dynamics that suggests an interacting potential dependent on particle orientation and stresses the decisive role played by particle surface heterogeneities. Building up on both such experimental results, the important role of air nanobubbles pinned on the particle interface is discussed.