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Hypothesis: The complexation of microgels with rigid nanoparticles is an effective way to impart novel properties and functions to the resulting hybrid particles for applications such as in optics, catalysis, or for the stabilization of foams/emulsions. The nanoparticles affect the conformation of the polymer network, both in bulk aqueous environments and when the microgels are adsorbed at a fluid interface, in a non-trivial manner by modulating the microgel size, stiffness and apparent contact angle., Experiments: Here, we provide a detailed investigation, using light scattering, in-situ atomic force microscopy and nano-indentation experiments, of the interaction between poly(N-isopropylacrylamide) microgels and hydrophobized silica nanoparticles after mixing in aqueous suspension to shed light on the network reorganization upon nanoparticle incorporation., Findings: The addition of nanoparticles decreases the microgels' bulk swelling and thermal response. When adsorbed at an oil-water interface, a higher ratio of nanoparticles influences the microgel's stiffness as well as their hydrophobic/hydrophilic character by increasing their effective contact angle, consequently modulating the monolayer response upon interfacial compression. Overall, these results provide fundamental understanding on the complex conformation of hybrid microgels in different environments and give inspiration to design new materials where the combination of a soft polymer network and nanoparticles might result in additional functionalities., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Inc. All rights reserved.)

Hypothesis: Particle surface chemistry and internal softness are two fundamental parameters in governing the mechanical properties of dense colloidal suspensions, dictating structure and flow, therefore of interest from materials fabrication to processing., Experiments: Here, we modulate softness by tuning the crosslinker content of poly(N-isopropylacrylamide) microgels, and we adjust their surface properties by co-polymerization with polyethylene glycol chains, controlling adhesion, friction and fuzziness. We investigate the distinct effects of these parameters on the entire mechanical response from restructuring to complete fluidization of jammed samples at varying packing fractions under large-amplitude oscillatory shear experiments, and we complement rheological data with colloidal-probe atomic force microscopy to unravel variations in the particles' surface properties., Findings: Our results indicate that surface properties play a fundamental role at smaller packings; decreasing adhesion and friction at contact causes the samples to yield and fluidify in a lower deformation range. Instead, increasing softness or fuzziness has a similar effect at ultra-high densities, making suspensions able to better adapt to the applied shear and reach complete fluidization over a larger deformation range. These findings shed new light on the single-particle parameters governing the mechanical response of dense suspensions subjected to deformation, offering synthetic approaches to design materials with tailored mechanical properties., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Inc. All rights reserved.)

Liposomes show promise as biolubricants for damaged cartilage, but their small size results in low joint and cartilage retention. We developed a zinc ion-based liposomal drug delivery system for local osteoarthritis therapy, focusing on sustained release and tribological protection from phospholipid lubrication properties. Our strategy involved inducing aggregation of negatively charged liposomes with zinc ions to extend rapamycin (RAPA) release and improve cartilage lubrication. Liposomal aggregation occurred within 10 min and was irreversible, facilitating excess cation removal. The aggregates extended RAPA release beyond free liposomes and displayed irregular morphology influenced by RAPA. At nearly 100 µm, the aggregates were large enough to exceed the previously reported size threshold for increased joint retention. Tribological assessment on silicon surfaces and ex vivo porcine cartilage revealed the system's excellent protective ability against friction at both nano- and macro-scales. Moreover, RAPA was shown to attenuate the fibrotic response in human OA synovial fibroblasts. Our findings suggest the zinc ion-based liposomal drug delivery system has potential to enhance OA therapy through extended release and cartilage tribological protection, while also illustrating the impact of a hydrophobic drug like RAPA on liposome aggregation and morphology., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: OD has/had consultancy relationship with and/or has received research funding from and/or has served as a speaker for the following companies in the last three calendar years: 4P-Pharma, Abbvie, Acceleron, Alcimed, Altavant, Amgen, AnaMar, Arxx, AstraZeneca, Blade, Bayer, Boehringer Ingelheim, Corbus, CSL Behring, Galderma, Galapagos, Glenmark, Gossamer, Horizon, Janssen, Kymera, Lupin, Medscape, Merck, Miltenyi Biotec, Mitsubishi Tanabe, Novartis, Pfizer, Prometheus, Redxpharma, Roivant and Topadur. Patent issued “mir-29 for the treatment of systemic sclerosis” (US8247389, EP2331143). PL has consulted and received research funding from Lipoid GmbH, Sanofi-Aventis Deutschland and DSM Nutritional Products Ltd., (Copyright © 2023 The Author(s). Published by Elsevier Inc. All rights reserved.)

The encapsulation of a rigid core within a soft polymeric shell allows obtaining composite colloidal particles that retain functional properties, e.g., optical or mechanical. At the same time, it favors their adsorption at fluid interfaces with a tunable interaction potential to realize tailored two-dimensional (2D) materials. Although they have already been employed for 2D assembly, the conformation of single particles, which is essential to define the monolayer properties, has been largely inferred via indirect or ex situ techniques. Here, by means of in situ atomic force microscopy experiments, the authors uncover the interfacial morphology of hard-core soft-shell microgels, integrating the data with numerical simulations to elucidate the role of the core properties, of the shell thicknesses, and that of the grafting density. They identify that the hard core can influence the conformation of the polymer shells. In particular, for the case of small shell thickness, low grafting density, or poor core affinity for water, the core protrudes more into the organic phase, and the authors observe a decrease in-plane stretching of the network at the interface. By rationalizing their general wetting behavior, such composite particles can be designed to exhibit specific inter-particle interactions of importance both for the stabilization of interfaces and for the fabrication of 2D materials with tailored functional properties., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The reconfiguration of individual soft and deformable particles upon adsorption at a fluid interface underpins many aspects of their dynamics and interactions, ultimately regulating the properties of monolayers of relevance for applications. In this work, we demonstrate that atomic force microscopy can be used for the in situ reconstruction of the three-dimensional conformation of model poly( N -isopropylacrylamide) microgels adsorbed at an oil-water interface. We image the particle topography from both sides of the interface to characterize its in-plane deformation and to visualize the occurrence of asymmetric swelling in the two fluids. In addition, the technique enables investigating different fluid phases and particle architectures, as well as studying the effect of temperature variations on particle conformation in situ. We envisage that these results open up an exciting range of possibilities to provide microscopic insights into the single-particle behavior of soft objects at fluid interfaces and into the resulting macroscopic material properties.

Dense suspensions of colloidal or granular particles can display pronounced non-Newtonian behaviour, such as discontinuous shear thickening and shear jamming. The essential contribution of particle surface roughness and adhesive forces confirms that stress-activated frictional contacts can play a key role in these phenomena. Here, by employing a system of microparticles coated by responsive polymers, we report experimental evidence that the relative contributions of friction, adhesion, and surface roughness can be tuned in situ as a function of temperature. Modifying temperature during shear therefore allows contact conditions to be regulated, and discontinuous shear thickening to be switched on and off on demand. The macroscopic rheological response follows the dictates of independent single-particle characterization of adhesive and tribological properties, obtained by colloidal-probe atomic force microscopy. Our findings identify additional routes for the design of smart non-Newtonian fluids and open a way to more directly connect experiments to computational models of sheared suspensions.

Herein, we introduce a method to locally modify the mechanical properties of a soft, biocompatible material through the exploitation of the effects induced by the presence of a local temperature gradient. In our hypotheses, this induces a concentration gradient in an aqueous sodium alginate solution containing calcium carbonate particles confined within a microfluidic channel. The concentration gradient is then fixed by forming a stable calcium alginate hydrogel. The process responsible for the hydrogel formation is initiated by diffusing an acidic oil solution through a permeable membrane in a 2-layer microfluidic device, thus reducing the pH and freeing calcium ions. We characterize the gradient of mechanical properties using atomic force microscopy nanoindentation measurements for a variety of material compositions and thermal conditions. Significantly, our novel approach enables the creation of steep gradients in mechanical properties (typically between 10-100 kPa/mm) on small scales, which will be of significant use in a range of tissue engineering and cell mechanosensing studies.

The development and application of nanofibres requires a thorough understanding of the mechanical properties on a single fibre level including respective modelling tools for precise fibre analysis. This work presents a mechanical and morphological study of poly-l-lactide nanofibres developed by needleless electrospinning. Atomic force microscopy (AFM) and micromechanical testing (MMT) were used to characterise the mechanical response of the fibres within a diameter range of 200-1400 nm. Young's moduli E determined by means of both methods are in sound agreement and show a strong increase for thinner fibres below a critical diameter of 800 nm. Similar increasing trends for yield stress and hardening modulus were measured by MMT. Finite element analyses show that the common practice of modelling three-point bending tests with either double supported or double clamped beams is prone to significant bias in the determined elastic properties, and that the latter is a good approximation only for small diameters. Therefore, an analytical formula based on intermediate boundary conditions is proposed that is valid for the whole tested range of fibre diameters, providing a consistently low error in axial Young's modulus below 10%. The analysis of fibre morphology by differential scanning calorimetry and 2D wide-angle X-ray scattering revealed increasing polymer chains alignment in the amorphous phase and higher crystallinity of fibres for decreasing diameter. The combination of these observations with the mechanical characterisation suggests a linear relationship between Young's modulus and both crystallinity and molecular orientation in the amorphous phase. STATEMENT OF SIGNIFICANCE: Fibrous membranes have rapidly growing use in various applications, each of which comes with specific property requirements. However, the development and production of nanofibre membranes with dedicated mechanical properties is challenging, in particular with techniques suitable for industrial scales such as needleless electrospinning. It is therefore a key step to understand the mechanical and structural characteristics of single nanofibres developed in this process, and to this end, the present work presents changes of internal fibre structure and mechanical properties with diameter, based on dedicated models. Special attention was given to the commonly used models for analyzing Young's modulus of single nanofibers in three-point bending tests, which are shown to be prone to large errors, and an improved robust approach is proposed., (Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

Surface roughness affects many properties of colloids, from depletion and capillary interactions to their dispersibility and use as emulsion stabilizers. It also impacts particle-particle frictional contacts, which have recently emerged as being responsible for the discontinuous shear thickening (DST) of dense suspensions. Tribological properties of these contacts have been rarely experimentally accessed, especially for nonspherical particles. Here, we systematically tackle the effect of nanoscale surface roughness by producing a library of all-silica, raspberry-like colloids and linking their rheology to their tribology. Rougher surfaces lead to a significant anticipation of DST onset, in terms of both shear rate and solid loading. Strikingly, they also eliminate continuous thickening. DST is here due to the interlocking of asperities, which we have identified as "stick-slip" frictional contacts by measuring the sliding of the same particles via lateral force microscopy (LFM). Direct measurements of particle-particle friction therefore highlight the value of an engineering-tribology approach to tuning the thickening of suspensions., Competing Interests: The authors declare no conflict of interest., (Copyright © 2018 the Author(s). Published by PNAS.)