Wetting Transition on Hydrophobic Surfaces Covered by Polyelectrolyte Brushes

International audienceWe study the wetting by water of complex “hydrophobic-hydrophilic” surfaces made of a hydrophobic substrate covered by a hydrophilic polymer brush. Polystyrene (PS) substrates covered with polystyrene-block-poly(acrylic acid) PS-b-PAA diblock copolymer layers were fabricated by Langmuir-Schaefer depositions and analyzed by atomic force microscopy (AFM) and ellipsometry. On bare PS substrate, we measured advancing angles θA ) 93 ( 1° and receding angles θR ) 81 ( 1°. On PS covered with poorly anchored PS-b-PAA layers, we observed large contact angle hysteresis, θA ≈ 90° and θR ≈ 0°, that we attributed to nanometric scale dewetting of the PS-b-PAA layers. On well-anchored PS-b-PAA layers that form homogeneous PAA brushes, a wetting transition from partial to total wetting occurs versus the amount deposited: both θA and θR decrease close to zero. A model is proposed, based on the Young-Dupre´ equation, that takes into account the interfacial pressure of the brush Π, which was determined experimentally, and the free energy of hydration of the polyelectrolyte monomers ΔGPAA hyd , which is the only fitting parameter. With ΔGPAA hyd ≈ -1300 J/mol, the model renders the wetting transition for all samples and explains why the wetting transition depends mainly on the average thickness of the brush and weakly on the length of PAA chains

pH/Temperature control of interpolymer complexation between poly(acrylic acid) and weak polybases in aqueous solutions

International audienc

Bioinspired microstructures of chitosan hydrogel provide enhanced wear protection

We describe the fabrication of physical chitosan hydrogels exhibiting a layered structure. This bilayered structure, as shown by SEM and confocal microscopy, is composed of a thin dense superficial zone (SZ), covering a deeper zone (DZ) containing microchannels orientated perpendicularly to the SZ. We show that such structure favors diffusion of macromolecules within the hydrogel matrix up to a critical pressure, σc, above which channels were constricted. Moreover, we found that the SZ provided a higher wear resistance than the DZ which was severely damaged at a pressure equal to the elastic modulus of the gel. The coefficient of friction (CoF) of the SZ remained independent of the applied load with μSZ = 0.38 ± 0.02, while CoF measured at DZ exhibited two regimes: an initial CoF close to the value found on the SZ, and a CoF that decreased to μDZ = 0.18 ± 0.01 at pressures higher than the critical pressure σc. Overall, our results show that internal structuring is a promising avenue in controlling and improving the wear resistance of soft materials such as hydrogels

Lubrication and wear protection of micro-structured hydrogels using bioinspired fluids

We report the fabrication and the use of a bioinspired synovial fluid acting as a lubricant fluid and anti-wear agent at soft and porous chitosan hydrogel tribopairs. This synthetic synovial fluid is composed of sodium hyaluronate (HA) and a bottle-brush polymer (BB) having a polycationic attachment group and polyzwitterionic pendant chains. 2.5 %w/w chitosan hydrogel plugs are organized in a bilayered structure exposing a thin and dense superficial zone (SZ), covering a porous deep zone (DZ) and exhibiting microchannels perpendicularly aligned to the SZ. Using a low-load tribometer, the addition of HA lubricating solution at the hydrogel-hydrogel rubbing contact drastically decreased the coefficient of friction (CoF) from μ = 0.20 ± 0.01 to μ = 0.04 ± 0.01 on the DZ configuration and from μ = 0.31 ± 0.01 to μ = 0.08 ± 0.01 on the SZ surface when increasing HA concentration from 0 to 1000 μg/mL and its molecular mass from 10 to 1500 kDa, similar to what was found when using BB polymer alone. When combining the BB polymer and the 1500 kDa HA, the CoF remained stable at μ = 0.04 ± 0.01 for both studied contact configurations, highlighting the synergistic interaction of the two macromolecules. Hydrogel wear was characterized by assessing the final gel surface roughness by the means of an interferometer. Increasing HA concentration and molecular weight plus the addition of BB polymer lead to a dramatic surface wear protection with a final gel surface roughness of the hydrogels similar to the untested gels. In brief, BB polymer in combination with high molecular weight HA is a potential lubricating fluid as well as a wear resistant agent for soft materials lubrication and wear protection

Intermolecular interactions between Bottlebrush Polymers boost the protection of surfaces against frictional wear

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of materials, copyright American Chemical Society after peer review and technical editing by the publisher."Polymers exhibiting the bottlebrush (BB) architecture have excellent lubricating properties. However, to motivate their use in real life systems, they must also protect surfaces against frictional damage. In this article, we synthesized a library of polyzwiterrionic bottlebrush polymers of different architectures to explore the effect of intermolecular interactions on their conformation at interfaces and their tribological properties. Using the surface forces apparatus, we show that increasing the number of adhesive blocks on the BB polymers does not impact the friction coefficient on mica surfaces, μ, which remained close to μ = 0.02 but drastically increased the threshold pressure, P*, at which wear initiates from P* = 0.4 ± 0.1 up to 8.0 ± 0.8 MPa. In mixtures of high molecular weight hyaluronic acid and BB polymers, a synergistic interaction between polymers occurred, leading to a significant increase in P*, independently of the BB polymer tested and even reaching superprotection for strongly interacting polymers (up to P* > 14 MPa). Overall, these results show that strong intermolecular interaction between BB polymers and high molecular weight linear polymers is a promising strategy to create highly protective lubricants

Where is VALDO? VAscular Lesions Detection and segmentatiOn challenge at MICCAI 2021

Imaging markers of cerebral small vessel disease provide valuable information on brain health, but their manual assessment is time-consuming and hampered by substantial intra- and interrater variability. Automated rating may benefit biomedical research, as well as clinical assessment, but diagnostic reliability of existing algorithms is unknown. Here, we present the results of the VAscular Lesions DetectiOn and Segmentation (Where is VALDO?) challenge that was run as a satellite event at the international conference on Medical Image Computing and Computer Aided Intervention (MICCAI) 2021. This challenge aimed to promote the development of methods for automated detection and segmentation of small and sparse imaging markers of cerebral small vessel disease, namely enlarged perivascular spaces (EPVS) (Task 1), cerebral microbleeds (Task 2) and lacunes of presumed vascular origin (Task 3) while leveraging weak and noisy labels. Overall, 12 teams participated in the challenge proposing solutions for one or more tasks (4 for Task 1-EPVS, 9 for Task 2-Microbleeds and 6 for Task 3-Lacunes). Multi-cohort data was used in both training and evaluation. Results showed a large variability in performance both across teams and across tasks, with promising results notably for Task 1-EPVS and Task 2-Microbleeds and not practically useful results yet for Task 3-Lacunes. It also highlighted the performance inconsistency across cases that may deter use at an individual level, while still proving useful at a population level

Specialist laboratory networks as preparedness and response tool - The emerging viral diseases-expert laboratory network and the chikungunya outbreak, Thailand, 2019

We illustrate the potential for specialist laboratory networks to be used as preparedness and response tool through rapid collection and sharing of data. Here, the Emerging Viral Diseases-Expert Laboratory Network (EVD-LabNet) and a laboratory assessment of chikungunya virus (CHIKV) in returning European travellers related to an ongoing outbreak in Thailand was used for this purpose. EVD-LabNet rapidly collected data on laboratory requests, diagnosed CHIKV imported cases and sequences generated, and shared among its members and with the European Centre for Disease Prevention and Control. Data across the network showed an increase in CHIKV imported cases during 1 October 2018-30 April 2019 vs the same period in 2018 (172 vs 50), particularly an increase in cases known to be related to travel to Thailand (72 vs 1). Moreover, EVD-LabNet showed that strains were imported from Thailand that cluster with strains of the ECSA-IOL E1 A226 variant emerging in Pakistan in 2016 and involved in the 2017 outbreaks in Italy. CHIKV diagnostic requests increased by 23.6% between the two periods. The impact of using EVD-LabNet or similar networks as preparedness and response tool could be improved by standardisation of the collection, quality and mining of data in routine laboratory management systems

Subcortical brain volume, regional cortical thickness, and cortical surface area across disorders: findings from the ENIGMA ADHD, ASD, and OCD Working Groups

Objective Attention-deficit/hyperactivity disorder (ADHD), autism spectrum disorder (ASD), and obsessive-compulsive disorder (OCD) are common neurodevelopmental disorders that frequently co-occur. We aimed to directly compare all three disorders. The ENIGMA consortium is ideally positioned to investigate structural brain alterations across these disorders. Methods Structural T1-weighted whole-brain MRI of controls (n=5,827) and patients with ADHD (n=2,271), ASD (n=1,777), and OCD (n=2,323) from 151 cohorts worldwide were analyzed using standardized processing protocols. We examined subcortical volume, cortical thickness and surface area differences within a mega-analytical framework, pooling measures extracted from each cohort. Analyses were performed separately for children, adolescents, and adults using linear mixed-effects models adjusting for age, sex and site (and ICV for subcortical and surface area measures). Results We found no shared alterations among all three disorders, while shared alterations between any two disorders did not survive multiple comparisons correction. Children with ADHD compared to those with OCD had smaller hippocampal volumes, possibly influenced by IQ. Children and adolescents with ADHD also had smaller ICV than controls and those with OCD or ASD. Adults with ASD showed thicker frontal cortices compared to adult controls and other clinical groups. No OCD-specific alterations across different age-groups and surface area alterations among all disorders in childhood and adulthood were observed. Conclusion Our findings suggest robust but subtle alterations across different age-groups among ADHD, ASD, and OCD. ADHD-specific ICV and hippocampal alterations in children and adolescents, and ASD-specific cortical thickness alterations in the frontal cortex in adults support previous work emphasizing neurodevelopmental alterations in these disorders

Adhésion stimulable d'hydrogels

The tunable adhesion of hydrogels on surfaces has systematically been studied by using specific and reversible polymer-polymer interactions. To this end, model surfaces of poly(acrylic acid) (PAA) brushes were obtained by "grafting to" and their structure, which is pH-sensitive, was characterized by neutron reflectivity. Meanwhile, neutral hydrogels of poly(N,N-dimethylacrylamide) (PDMA) and poly(acrylamide) (PAM) were synthesized by conventional radical polymerization, and their mechanical properties, their structure and their swelling were studied and varied by the means of two parameters: the initial swelling and the cross-linking density. In aqueous solution, the polymeric pairs of PAA and PDMA or PAA and PAM form interpolymer complexes. Their formation depends on pH and temperature and was studied by turbidimetry. Associations occur at low pH in both cases, and even if the two polymeric pairs are chemically similar, their complexations correspond to a standard UCST-type phase transition when the the proton acceptor is PAM but to an LCST-type transition with PDMA. The formation of these complexes in solution was also studied at the interfaces between the PAA brush and the PDMA and PAM hydrogels. The swelling behavior of the brush was investigated by neutron reflectivity: in the presence of the gel, the brush is additionally stretched in the presence of interactions at low pH and its structure remains unperturbed at high pH. A macroscopic study of these interactions at interfaces was carried out by the development of an experimental setup and protocols suitable for the quantitative measurement of the adhesion energy between immersed materials. Using a flat-flat contact test between the PAA brushes and PDMA and PAM gels covalently attached to substrates, an immersed and pH-tunable adhesion of the magnitude of thermodynamic adhesions has been demonstrated as well as the relatively slow kinetics involved in the formation and rupture of the interpolymer complexes at interfaces.L'adhésion stimulable d'un hydrogel sur une surface a été étudiée de façon systématique par le jeu d'interactions spécifiques réversibles entre polymères. A cette fin, des surfaces modèles de brosses de poly(acide acrylique) (PAA) ont été obtenues par " grafting to " et leur structure, sensible au pH, a été caractérisée par réflectivité de neutrons. Parallèlement, des hydrogels neutres de poly(N,N-diméthylacrylamide) (PDMA) et de poly(acrylamide) (PAM) ont été synthétisés par polymérisation radicalaire conventionnelle ; leurs propriétés mécaniques, leur structure et leur gonflement ont été étudiés et variés au moyen de deux paramètres : le gonflement initial et le taux de réticulant. En solution aqueuse, les couples de polymères PAA et PDMA ou PAA et PAM forment des complexes inter polymères dont l'apparition dépend du pH et de la température. Les associations se produisent à pH faible dans les deux cas ; et quoique relativement similaire d'un point de vue chimique, ces couples de polymères s'associent par une séparation de phase de type UCST lorsque l'accepteur de proton est le PAM, mais par une transition de type LCST avec le PDMA. La formation de ces complexes en solution a aussi été étudiée aux interfaces entre la brosse de PAA et les hydrogels de PDMA et PAM. Une étude à l'échelle de la brosse a été menée par réflectivité de neutrons : en présence de gel, un gonflement additionnel de la brosse est observé en présence des interactions à faible pH alors que sa structure n'est pas perturbée à pH élevé. L'étude macroscopique de ces interactions aux interfaces correspond aux tests d'adhésion : un montage expérimental et des protocoles adaptés à la mesure quantitative de l'énergie d'adhésion entre matériaux immergés. Au moyen d'un contact plan-plan entre les brosses de PAA et les gels de PDMA et PAM attachés de façon covalente sur des substrats, une adhésion immergée stimulable par le pH de l'ordre de grandeur des adhésions thermodynamiques a été mise en évidence, de même que les cinétiques relativement lentes impliquées dans la formation et la rupture des complexes aux interfaces

Remplacement valvulaire aortique percutané (TAVI) (intérêt pronostique de l'évaluation gériatrique en pré-procédure)

LILLE2-BU Santé-Recherche (593502101) / SudocSudocFranceF