Ref HAL: hal-03345301_v1
DOI: 10.1122/8.0000304
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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.

Ref HAL: hal-03341513_v1
DOI: 10.1073/pnas.2109560118
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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.

Ref HAL: hal-03333988_v1
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The development of smart nanomaterials has attracted great attention in several fields like nanoscience and nanotechnology due to their unique response to external stimuli. Many of them are based on polymers that can exhibit a shape-changes when submitted to environmental modifications. Poly(N-isopropylacrylamide), PNIPAM, is a thermo-responsive polymer. Linear chains are water soluble at room temperature but undergo a reversible coil-to-globule transition at a lower critical solution temperature (LCST) close to 32°C due to the dehydration and subsequent collapse of its chains into compact globules. [1] This phenomenon results in a volume phase transition (VPT) in PNIPAM based crosslinked microgels and can be used to promote original thermal effects.Hybrid nanocomposite microgels associating PNIPAM and gold nanoparticles (GNP) have thus been designed in order to take advantage of the outstanding plasmonic and photo-thermal properties of GNP to promote the VPT of the microgels through an efficient photo-thermal conversion. [2] With their strong diameter-dependent optical absorption in the near infrared (NIR) and their large surface area favoring photo-thermal transfer, semiconducting single-walled carbon nanotubes (s-SWNT) are also good candidates for photo-thermal conversion in the NIR (Figure 1a). However, to the best of our knowledge, no thorough studies of nanomaterials based on both SWNT and PNIPAM have been reported so far.Here we describe the preparation of SWNT/PNIPAM hybrid microgels through a non-covalent functionalization technique. These nanoparticles are stable in water and show a VPT, which can be promoted either by direct heating or by excitation of the resonant absorption of s-SWNT in the NIR (Figure 1b-c). The photoluminescence (PL) signal can be used to monitor the VPT by a redshift observed when crossing the LCST, while the Raman signatures remain essentially the same.

Ref HAL: hal-03333981_v1
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Avec la plupart des couches d’alignement classiques des cellules commerciales, il est difficile d’obtenir une texture uniforme des phases nématiques twist bend (NTB) en géométrie planaire, y compris dans des cellules très fines (~1 μm). Même lorsqu’un composé présente une phase nématique N bien alignée, on observe en effet la formation spontanée de bandes lorsque l’on passe en phase NTB [1,2,3] (voir Fig.1-a). Cette texture en rayures est caractérisée par un pas égal à deux fois l’épaisseur de la cellule [1]. Son origine est attribuée à l’amincissement rapide des pseudo-couches NTB en dessous de la température de transition N-NTB qui conduit à une instabilité d’ondulation.Nous avons étudié en détail le rôle de la force d’ancrage des couches d’alignement sur les textures NTB d’un dimère cyanophyphényle, le CB7CB (1,7-bis-4-(4-cyanobiphenyl) heptane). Pour cela nous avons utilisé un polymère dont la force d’ancrage sur les nématiques cyanobiphényles (monomères) était connue pour varier fortement selon les conditions de préparation. Une étude systématique de l’ancrage de ce polymère sur le CB7CB a été faite en phase nématique et nous avons étudié l’influence des énergies d’ancrages zénithale et azimutale sur les textures obtenues en phase NTB. Dans des cellules symétriques, nous avons ainsi montré que la périodicité des instabilités dépendait fortement de l’ancrage et notamment de sa composante azimutale.Par ailleurs, ce travail a permis de montrer qu’avec des conditions d’ancrage adéquates, il était possible d’obtenir un alignement spontané uniforme de la phase NTB (voir Fig.1-b-c). Cet alignement est conservé même en s’éloignant de la température de transition, ouvrant la possibilité future d’utiliser les phases NTB dans des dispositifs électro-optiques.

Ref HAL: hal-03328307_v1
PMID 34454365
DOI: 10.1016/j.colsurfb.2021.112054
WoS: 000702833400006
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14 Citations
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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.

Ref HAL: hal-03324137_v1
Ref Arxiv: 2107.13348
DOI: 10.1063/5.0057316
WoS: 000691864900008
Ref. & Cit.: NASA ADS
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2 Citations
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When a drop of fluid hits a small solid target of comparable size, it expands radially until reaching a maximum diameter and subsequently recedes. In this work, we show that the expansion process of liquid sheets is controlled by a combination of shear (on the target) and biaxial extensional (in the air) deformations. We propose an approach toward a rational description of the phenomenon for Newtonian and viscoelastic fluids by evaluating the viscous dissipation due to shear and extensional deformations, yielding a prediction of the maximum expansion factor of the sheet as a function of the relevant viscosity. For Newtonian systems, biaxial extensional and shear viscous dissipation are of the same order of magnitude. On the contrary, for thinning solutions of supramolecular polymers, shear dissipation is negligible compared to biaxial extensional dissipation and the biaxial thinning extensional viscosity is the appropriate quantity to describe the maximum expansion of the sheets. Moreover, we show that the rate-dependent biaxial extensional viscosities deduced from drop impact experiments are in good quantitative agreement with previous experimental data and theoretical predictions for various viscoelastic liquids.

Ref HAL: hal-03322429_v1
DOI: 10.1021/acsanm.1c00803
WoS: WOS:000668366800031
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Herein, we demonstrate that tuning of structural parameters and material chemistry enables control of the permeability and selectivity of gases (CO2, He, and CH4) in membranes based on poly(butyl methacrylate)-grafted nanoparticles (PGNs). Our data show that the presence of nanoparticles and the overall dense packing of grafted chains noticeable in PGNs with low grafting density have an adverse effect on the diffusivity of gases. This effect is compensated by an improvement in the solubility of CO2 gas promoted by the silica nanoparticle surface, yielding a substantial improvement in the permeability of CO2 versus CH4. In membranes with high grafting density, changes in the structural arrangements and alterations in the membrane porosity, evident from small-angle X-ray scattering and positron annihilation lifetime spectroscopy, positively influence the permeability of He and CO2 gases. In contrast, CH4 permeability in the same membranes is significantly suppressed, suggesting the formation of a unique, highly selective environment for gas separation. As a result, an improvement of up to 50% in selectivity for gas pairs containing large CH4 molecules is observed. Our studies provide fundamental insights into the role that structural parameters play in gas transport through polymer membranes, laying a foundation for the rational design of membranes with improved permeability and selectivity.