The present paper deals with the correlation between intramolecular and intermolecular interactions of polycarboxybetaines. The degree of coupling between the opposite charges within the polycarboxybetaine molecules was varied by spacers of different length and bythe substitution of additional alkyl chains at the quaternary nitrogen atom. In order to check intermolecular interactions between polycarboxybetaines, SANS measurements were carried out at aqueous polycarboxybetaines solutions. For getting information about the interaction with an oppositely charged polyelectrolyte, multilayers were formed by alternating adsorption of polystyrene sulfonate (PSS) and polycarboxybetaines from aqueous solutions. The occurrence of a structure peak in SANS spectra and the ability to form polyelectrolytemultilayers provide an indicator for the polyelectrolyte character of some of the studied polycarboxybetaines. Not only the charge but also the hydrophobicity of the polycarboxybetaines has a pronounced effect on the chain conformation and therefore on the thickness of the polyelectrolyte multilayers. The results show that small differences in molecular architecture lead to pronounced differences in intermolecular interactions.

Aggregation mechanisms of amyloid β peptides depend on multiple intrinsic and extrinsic physicochemical factors (e.g., peptide chain length, truncation, peptide concentration, pH, ionic strength, temperature, metal concentration, etc.). Due to this high number of parameters, the formation of oligomers and their propensity to aggregate make the elucidation of this physiopathological mechanism a challenging task. From the analytical point of view, up to our knowledge, few techniques are able to quantify, in real time, the proportion and the size of the different soluble species during the aggregation process. This work aims at demonstrating the efficacy of the modern Taylor dispersion analysis (TDA) performed in capillaries (50 μm i.d.) to unravel the speciation of β-amyloid peptides in low-volume peptide samples (∼100 μL) with an analysis time of ∼3 min per run. TDA was applied to study the aggregation process of Aβ(1-40) and Aβ(1-42) peptides at physiological pH and temperature, where more than 140 data points were generated with a total volume of ∼1 μL over the whole aggregation study (about 0.5 μg of peptides). TDA was able to give a complete and quantitative picture of the Aβ speciation during the aggregation process, including the sizing of the oligomers and protofibrils, the consumption of the monomer, and the quantification of different early- and late-formed aggregated species.

The adsorption of a sunflower protein extract at two air− water and oil−water interfaces is investigated using tensiometry, dilational viscoelasticity, and ellipsometry. For both interfaces, a three step mechanism was evidenced thanks to master curve representations of the data taken at different aging times and protein concentrations. At short times, a diffusion limited adsorption of proteins at interfaces is demonstrated. First, a two-dimensional protein film is formed with a partition of the polypeptide chains in the two phases that depends strongly on the nature of the hydrophobic phase: most of the film is in the aqueous phase at the air−water interface, while it is mostly in the organic phase at the oil−water interface. Then a three-dimensional saturated monolayer of proteins is formed. At short times, adsorption mechanisms are analogous to those found with typical globular proteins, while strong divergences are observed at longer adsorption times. Following the saturation step, a thick layer expands in the aqueous phase and appears associated with the release of large objects in the bulk. The kinetic evolution of this second layer is compatible with a diffusion limited adsorption of the minor population of polymeric complexes with hydrodynamic radius R H ∼ 80 nm, evidenced in equilibrium with hexameric globulins (R H ∼ 6 nm) in solution. These complexes could result from the presence of residual polyphenols in the extract and raise the question of the role of these compounds in the interfacial properties of plant protein extracts.

We report on the response of semi-dilute shear-banding wormlike micelles to time-dependent flow protocols such as step stress and shear startup. We use global rheology coupled to direct optical visualisations in Taylor-Couette flow to provide a detailed 2D description of the spatio-temporal dynamics of the shear banding flow under imposed stress. We compare these dynamics to their extensively studied counterpart under imposed shear rate. We show that, for a given asymptotic state, the onset of banding is delayed and the transients are longer when the stress is used as control parameter. The way the banding structure is built up strongly depends on the control parameter. In the two cases, secondary flows develop on top of the shear-banding instability: after shear startup, the interface between bands is formed in the bulk of the system and migrates inwards to its stationary position in the gap of the Taylor-Couette device, before being destabilized due to elastic instability; under creep flow, the interface between bands forms at the inner wall and becomes wavy while it is still migrating outwards to its steady position, leading to permanent rearrangements of the flow structure until steady state is reached, potentially explaining longer transients. We also outline the possible mechanical signature of the onset of shear banding in terms of shape of the bulk mechanical signals, which is the subject of the second part of this work [Briole et al., submitted].

Complex systems often exhibit shear banding-the coexistence of two different states characterized by their internal structuring and local shear rates. For some of them, the heterogeneous flow corresponds to the final steady state response while for others, shear banding can only be transient, the banding structure healing back to homogeneous flow in the ultimate steady state after long-lived periods. In order to explain the diversity of observations, Moorcroft and Fielding have established general criteria for the onset of banding in time-dependent flows of complex systems, ranging from polymeric fluids to soft glassy materials [Moorcroft et al., Phys. Rev. Lett., 2013, 110, 086001]. The proposed criteria are based on the time evolution of the bulk rheological response function of the system to a given time-dependent flow protocol and are associated with a specific signature in the mechanical response. In this contribution, we test the validity of these criteria in the case of two common time-dependent flow protocols: a step stress and a shear startup. Two types of fluids are examined. On the one hand, a wormlike micelles system exhibiting steady shear banding is studied experimentally, using rheometry coupled with direct visualisations and particle image velocimetry. On the other hand, we analyse previous literature on yield stress fluids exhibiting transient shear banding. Under creep flow, for both types of fluids the onset of banding arises in a time window compatible with the Moorcroft-Fielding criterion. However, the mechanical signature, i.e. the shape of the bulk mechanical signal as a function of time is not the one expected within some of the specific models with which the general Moorcroft-Fielding criteria were tested numerically. Under shear startup, both types of fluids behave differently. The criterion holds for yield stress fluids, the onset of banding arising just after the stress overshoot, as expected. On the contrary, for wormlike micelles the window of instability is delayed, even if the overshoot clearly plays a crucial role in the nucleation of the shear-induced structures. Regardless of the flow protocol or the system, wall slip seems to go hand in hand with banding indicating that it is a key ingredient to take into account.

Thermoresponsive microgels are one of the most investigated types of soft colloids, thanks to their ability to undergo a VolumePhase Transition (VPT) close to ambient temperature. However, this fundamental phenomenon still lacks a detailed microscopicunderstanding, particularly regarding the presence and the role of charges in the deswelling process. This is particularly important for the widely used poly(N-isopropylacrylamide)–based microgels, where the constituent monomers are neutral but charged groups arise due to the initiator molecules used in the synthesis. Here, we address this point combining experiments with state-of-the-art simulations to show that the microgel collapse does not happen in a homogeneous fashion, but through a two-step mechanism, entirely attributable to electrostatic effects.The signature of this phenomenon is the emergence of a minimum in the ratio between gyration and hydrodynamic radii at the VPT. Thanks to simulations of microgels with different cross-linker concentrations, charge contents, and charge distributions, we provide evidence that peripheral charges arising from the synthesis are responsible for this behavior and we further build a universal master curve able to predict the twostep deswelling. Our results have direct relevance on fundamental soft condensed matter science and on applications where microgels are involved, ranging from materials to biomedical technologies.

Isoniazid (INH) is one of the primary drugs used in tuberculosis treatment and its encapsulation in liposomal vesicles can both improve its therapeutic index and minimize toxicity. Here we consider mixtures of hydrogenated soy phosphatidylcholine-phosphatidylglycerol (HSPC-DPPG) to get novel biocompatible liposomes for INH delivery. We determined INH encapsulation efficiency by coupling for the first time UV and Laser Transmission Spectroscopy and we showed that HSPC-DPPG liposomes can load more INH than expected from simple geometrical arguments, thus suggesting the presence of drug-lipid association. To focus on this aspect, which has never been explored in liposomal formulations, we employed several complementary techniques, such as dynamic and static light scattering, calorimetry and surface pressure measurements on lipid monolayers. We find that INH-lipid interaction increases the entrapment capability of liposomes due to INH adsorption. Moreover, the preferential INH-HSPC dipole-dipole interaction promotes the modification of lipid ordering, favoring the formation of HSPC-richer domains in excess of DPPG. Our findings highlight how investigating the fundamental aspects of drug-lipid interactions is of paramount importance for the optimal design of liposomal nanocarriers.