Toward vanishing droplet friction on repellent surfaces.

Superhydrophobic surfaces are often seen as frictionless materials, on which water is highly mobile. Understanding the nature of friction for such water-repellent systems is central to further minimize resistance to motion and energy loss in applications. For slowly moving drops, contact-line friction has been generally considered dominant on slippery superhydrophobic surfaces. Here, we show that this general rule applies only at very low speed. Using a micropipette force sensor in an oscillating mode, we measure the friction of water drops approaching or even equaling zero contact-line friction. We evidence that dissipation then mainly stems from the viscous shearing of the air film (plastron) trapped under the liquid. Because this force is velocity dependent, it can become a serious drag on surfaces that look highly slippery from quasi-static tests. The plastron thickness is found to be the key parameter that enables the control of this special friction, which is useful information for designing the next generation of ultraslippery water-repellent coatings.

pH-Responsive Near-Infrared Emitting Gold Nanoclusters.

Near-infrared (NIR) fluorophores with pH-responsive properties suggest merits in biological analyses. This work establishes a general and effective method to obtain pH-responsive NIR emissive gold nanoclusters by introducing aliphatic tertiary amine (TA) groups into the ligands. Computational study suggests that the pH-responsive NIR emission is associated with electronic structure change upon protonation and deprotonation of TA groups. Photo-induced electron transfer between deprotonated TA groups and the surface Au-S motifs of gold nanoclusters can disrupt the radiative transitions and thereby decrease the photoluminescence intensity in basic environments (pH=7-11). By contrast, protonated TA groups curb the electron transfer and restore the photoluminescence intensity in acidic environments (pH=4-7). The pH-responsive NIR-emitting gold nanoclusters serve as a specific and sensitive probe for the lysosomes in the cells, offering non-invasive emissions without interferences from intracellular autofluorescence.

Supercharged Fluorescent Protein-Apoferritin Cocrystals for Lighting Applications.

The application of fluorescent proteins (FPs) in optoelectronics is hindered by the need for effective protocols to stabilize them under device preparation and operational conditions. Factors such as high temperatures, irradiation, and organic solvent exposure contribute to the denaturation of FPs, resulting in a low device performance. Herein, we focus on addressing the photoinduced heat generation associated with FP motion and rapid heat transfer. This leads to device temperatures of approximately 65 °C, causing FP-denaturation and a subsequent loss of device functionality. We present a FP stabilization strategy involving the integration of electrostatically self-assembled FP-apoferritin cocrystals within a silicone-based color down-converting filter. Three key achievements characterize this approach: (i) an engineering strategy to design positively supercharged FPs (+22) without compromising photoluminescence and thermal stability compared to their native form, (ii) a carefully developed crystallization protocol resulting in highly emissive cocrystals that retain the essential photoluminescence features of the FPs, and (iii) a strong reduction of the device's working temperature to 40 °C, leading to a 40-fold increase in Bio-HLEDs stability compared to reference devices.

Long-term stability of aerophilic metallic surfaces underwater.

Aerophilic surfaces immersed underwater trap films of air known as plastrons. Plastrons have typically been considered impractical for underwater engineering applications due to their metastable performance. Here, we describe aerophilic titanium alloy (Ti) surfaces with extended plastron lifetimes that are conserved for months underwater. Long-term stability is achieved by the formation of highly rough hierarchically structured surfaces via electrochemical anodization combined with a low-surface-energy coating produced by a fluorinated surfactant. Aerophilic Ti surfaces drastically reduce blood adhesion and, when submerged in water, prevent adhesion of bacteria and marine organisms such as barnacles and mussels. Overall, we demonstrate a general strategy to achieve the long-term stability of plastrons on aerophilic surfaces for previously unattainable underwater applications.

Thermodynamically controlled multiphase separation of heterogeneous liquid crystal colloids.

Phase separation is a universal physical transition process whereby a homogeneous mixture splits into two distinct compartments that are driven by the component activity, elasticity, or compositions. In the current work, we develop a series of heterogeneous colloidal suspensions that exhibit both liquid-liquid phase separation of semiflexible binary polymers and liquid crystal phase separation of rigid, rod-like nanocellulose particles. The phase behavior of the multicomponent mixture is controlled by the trade-off between thermodynamics and kinetics during the two transition processes, displaying cholesteric self-assembly of nanocellulose within or across the compartmented aqueous phases. Upon thermodynamic control, two-, three-, and four-phase coexistence behaviors with rich liquid crystal stackings are realized. Among which, each relevant multiphase separation kinetics shows fundamentally different paths governed by nucleation and growth of polymer droplets and nanocellulose tactoids. Furthermore, a coupled multiphase transition can be realized by tuning the composition and the equilibrium temperature, which results in thermotropic behavior of polymers within a lyotropic liquid crystal matrix. Finally, upon drying, the multicomponent mixture undergoes a hierarchical self-assembly of nanocellulose and polymers into stratified cholesteric films, exhibiting compartmentalized polymer distribution and anisotropic microporous structure.

Magnetic Quincke rollers with tunable single-particle dynamics and collective states.

Electrohydrodynamically driven active particles based on Quincke rotation have quickly become an important model system for emergent collective behavior in nonequilibrium colloidal systems. Like most active particles, Quincke rollers are intrinsically nonmagnetic, preventing the use of magnetic fields to control their complex dynamics on the fly. Here, we report on magnetic Quincke rollers based on silica particles doped with superparamagnetic iron oxide nanoparticles. We show that their magnetic nature enables the application of both externally controllable forces and torques at high spatial and temporal precision, leading to several versatile control mechanisms for their single-particle dynamics and collective states. These include tunable interparticle interactions, potential energy landscapes, and advanced programmable and teleoperated behaviors, allowing us to discover and probe active chaining, anisotropic active sedimentation-diffusion equilibria, and collective states in various geometries and dimensionalities.

In-situ Monitoring of Photocontrollable Wrinkle Erasure in Azobenzene-based Supramolecular Systems.

In this contribution, dynamic photoinduced wrinkle erasure enabled by photomechanical changes in supramolecular polymer-azo complexes was characterized via confocal microscopy. Different photoactive molecules, disperse yellow 7 (DY7) and 4,4'-dihydroxyazobenzene (DHAB), were compared to 4-hydroxy-4'-dimethylaminoazobenzene (OH-azo-DMA). The characteristic erasure times of wrinkles were quickly assessed by using an image processing algorithm. The results confirm that the photoinduced movement on the topmost layer can be successfully transferred to the substrate. Furthermore, the chosen supramolecular strategy allows decoupling the effect of molecular weight of the polymer and photochemistry of the chromophore, allowing quantitative comparison of wrinkling erasure efficiency of different materials and providing a facile way to optimize the system for specific applications.

Compressibility and porosity modulate the mechanical properties of giant gas vesicles.

Gas vesicles used as contrast agents for noninvasive ultrasound imaging must be formulated to be stable, and their mechanical properties must be assessed. We report here the formation of perfluoro-n-butane microbubbles coated with surface-active proteins that are produced by filamentous fungi (hydrophobin HFBI from Trichoderma reesei). Using pendant drop and pipette aspiration techniques, we show that these giant gas vesicles behave like glassy polymersomes, and we discover novel gas extraction regimes. We develop a model to analyze the micropipette aspiration of these compressible gas vesicles and compare them to incompressible liquid-filled vesicles. We introduce a sealing parameter to characterize the leakage of gas under aspiration through the pores of the protein coating. Utilizing this model, we can determine the elastic dilatation modulus, surface viscosity, and porosity of the membrane. These results demonstrate the engineering potential of protein-coated bubbles for echogenic and therapeutic applications and extend the use of the pipette aspiration technique to compressible and porous systems.

Magnetic field-driven particle assembly and jamming for bistable memory and response plasticity.

Unlike classic synthetic stimulus-responsive and shape-memory materials, which remain limited to fixed responses, the responses of living systems dynamically adapt based on the repetition, intensity, and history of stimuli. Such plasticity is ubiquitous in biology, which is profoundly linked to memory and learning. Concepts thereof are searched for rudimentary forms of "intelligent materials." Here, we show plasticity of electroconductivity in soft ferromagnetic nickel colloidal supraparticles with spiny surfaces, assembling/disassembling to granular conducting micropillars between two electrodes driven by magnetic field B. Colloidal jamming leads to conduction hysteresis and bistable memory upon increasing and subsequently decreasing B. Abrupt B changes induce larger conduction changes than gradual B-changes. Periodic B pulsing drives to frequency-dependent facilitation or suppression of conductivity compared to exposing the same constant field. The concepts allow remotely controlled switching plasticity, illustrated by a rudimentary device. More generally, we foresee adaptive functional materials inspired by response plasticity and learning.

Recombinant protein condensation inside E. coli enables the development of building blocks for bioinspired materials engineering - Biomimetic spider silk protein as a case study.

Recombinant expression of proteins destined to form biological materials often results in poor production yields or loss of their function due to premature aggregation. Recently, liquid-liquid phase separation has been proposed as a mechanism to control protein solubility during expression and accumulation in the cytoplasm. Here, we investigate this process in vivo during the recombinant overexpression of the mimetic spider silk mini-spidroin NT2RepCT in Escherichia coli. The protein forms intracellular liquid-like condensates that shift to a solid-like state triggered by a decrease in their microenvironmental pH. These features are also maintained in the purified sample in vitro both in the presence of a molecular crowding agent mimicking the bacterial intracellular environment, and during a biomimetic extrusion process leading to fiber formation. Overall, we demonstrate that characterization of protein condensates inside E. coli could be used as a basis for selecting proteins for both materials applications and their fundamental structure-function studies.

Correction: ß-1,3-Glucan synthesis, novel supramolecular self-assembly, characterization and application.

Correction for 'ß-1,3-Glucan synthesis, novel supramolecular self-assembly, characterization and application' by Robert Pylkkänen et al., Nanoscale, 2022, https://doi.org/10.1039/D2NR02731C.

ß-1,3-Glucan synthesis, novel supramolecular self-assembly, characterization and application.

ß-1,3-Glucans are ubiquitously observed in various biological systems with diverse physio-ecological functions, yet their underlying assembly mechanism and multiscale complexation in vitro remains poorly understood. Here, we provide for the first-time evidence of unidentified ß-1,3-glucan supramolecular complexation into intricate hierarchical architectures over several length scales. We mediated these unique assemblies using a recombinantly produced ß-1,3-glucan phosphorylase (Ta1,3BGP) by fine-tuning solution conditions during particle nucleation and growth. We report a synthesis of interconnected parallel hexagonal lamellae composed of 8 nm thick sheets of highly expanded paracrystals. The architecture consists of ß-1,3-glucan triple-helices with considerable inter-intra hydrogen bonding within, as well as in between adjacent triple-helices. The results extend our understanding of ß-1,3-glucan molecular organization and shed light on different aspects of the crystallization processes of biomolecules into structures unseen by nature. The presented versatile synthesis yields new materials for diverse medical and industrial applications.

Dispersing swimming microalgae in self-assembled nanocellulose suspension: Unveiling living colloid dynamics in cholesteric liquid crystals.

Active matter comprises individual energy-consuming components that convert locally stored energy into mechanical motion. Among these, liquid crystal dispersed self-propelled colloids have displayed fascinating dynamic effects and nonequilibrium behaviors. In this work, we introduce a new type of active soft matter based on swimming microalgae and lyotropic nanocellulose liquid crystal. Cellulose is a kind of biocompatible polysaccharide that nontoxic to living biological colloids. In contrast to microalgae locomotion in isotropic and low viscosity media, we demonstrate that the propulsion force of swimming microalgae can overcome the stabilizing elastic force in cholesteric nanocellulose liquid crystal, with the displacement dynamics (gait, direction, frequency, and speed) be altered by the surrounding medium. Simultaneously, the active stress and shear flow exerted by swimming microalgae can introduce local perturbation in surrounding liquid crystal orientation order. The latter effect yields hydrodynamic fluctuations in bulk phase as well as layer undulations, helicoidal axis splay deformation and director bending in the cholesteric assembly, which finally followed by a recovery according to the inherent viscoelasticity of liquid crystal matrix. Our results point to an unorthodox design concept to generate a new type of hybrid soft matter that combines nontoxic cholesteric liquid crystal and active particles, which are expected to open opportunities in biosensing and biomechanical applications.

Fusion Dynamics of Hybrid Cell-Microparticle Aggregates: A Jelly Pearl Model.

We study the fusion of homogeneous cell aggregates and of hybrid aggregates combining cells and microparticles. In all cases, we find that the contact area does not vary linearly over time, as observed for liquid drops, but rather it follows a power law in t2/3. This result is interpreted by generalizing the fusion model of soft viscoelastic solid balls to viscoelastic liquid balls, akin to jelly pearls. We also explore the asymmetric fusion between a homogeneous aggregate and a hybrid aggregate. This latter experiment allows the determination of the self-diffusion coefficient of the cells in a tissue by following the spatial distribution of internalized particles in the cells.

Electroferrofluids with nonequilibrium voltage-controlled magnetism, diffuse interfaces, and patterns.

It has been recognized that driving matter to nonequilibrium states can lead to emergent behaviors and functionalities. Here, we show that uniform colloidal dispersions can be driven into dissipative nonuniform states with emerging behaviors. We experimentally demonstrate this with electrically driven weakly charged superparamagnetic iron oxide nanoparticles in a nonpolar solvent. The driving leads to formation of nonequilibrium concentration gradients that further translate to nonequilibrium magnetism, including voltage-controlled magnetization and susceptibility. The concentration gradients also serve as diffuse interfaces that respond to external magnetic fields, leading to novel dissipative patterns. We identify the closest nondissipative analogs, discuss the differences, and highlight the ability to directly quantify the dissipation and link it to the pattern formation. Beyond voltage-controlled magnetism, we foresee that the concept can be generalized to other functional colloids to create, e.g., optical, electrical, catalytic, and mechanical responses that are not possible in thermodynamic equilibrium.

Diversity of non-equilibrium patterns and emergence of activity in confined electrohydrodynamically driven liquids.

Spontaneous emergence of organized states in materials driven by non-equilibrium conditions is of notable fundamental and technological interest. In many cases, the states are complex, and their emergence is challenging to predict. Here, we show that an unexpectedly diverse collection of dissipative organized states emerges in a simple system of two liquids under planar confinement when driven by electrohydrodynamic shearing. At low shearing, a symmetry breaking at the liquid-liquid interface leads to a one-dimensional corrugation pattern. At slightly stronger shearing, topological changes give raise to the emergence of Quincke rolling filaments, filament networks, and two-dimensional bicontinuous fluidic lattices. At strong shearing, the system transitions into dissipating polygonal, toroidal, and active droplets that form dilute gas-like states at low densities and complex active emulsions at higher densities. The diversity of the observed dissipative organized states is exceptional, pointing toward non-equilibrium optical devices and new avenues in several fields of research.

Correction: Chlamydomonas reinhardtii swimming in the Plateau borders of 2D foams.

Correction for 'Chlamydomonas reinhardtii swimming in the Plateau borders of 2D foams' by Oskar Tainio et al., Soft Matter, 2021, 17, 145-152, DOI: 10.1039/D0SM01206H.

Chlamydomonas reinhardtii swimming in the Plateau borders of 2D foams.

Unicellular Chlamydomonas reinhardtii micro-algae cells were inserted into a quasi-2D Hele-Shaw chamber filled with saponin foam. The movement of the algae along the bubble borders was then manipulated and tracked. These self-propelled particles generate flow and stresses in their surrounding matter. In addition, the algae possess the capability of exerting forces that alter bubble boundaries while maintaining an imminent phototactic movement. We find that by controlling the gas fraction of the foam we can change the interaction of the algae and bubbles. Specifically, our data expose three distinct swimming regimes for the algae with respect to the level of confinement due to the Plateau border cross-section: unlimited bulk, transition, and overdamped regimes. At the transition regime we find the speed of the algae to be modeled by a simple force balance equation emerging from the shear inside the Plateau border. Thus, we have shown that it is possible to create an algae-friendly foam while controlling the algae motion. This opens doors to multiple applications where the flow of nutrients, oxygen and recirculation of living organisms is essential.

Viscosity-enhanced droplet motion in sealed superhydrophobic capillaries.

It is well known that an increased viscosity slows down fluid dynamics. Here we show that this intuitive rule is not general and can fail for liquids flowing in confined liquid-repellent systems. A gravity-driven, highly viscous glycerol droplet inside a sealed superhydrophobic capillary is moving more than 10 times faster than a water droplet with three-orders-of-magnitude lower viscosity. Using tracer particles, we show that the low-viscosity droplets are rapidly rotating internally, with flow velocities greatly exceeding the center-of-mass velocity. This is in stark contrast to the faster moving high-viscosity droplets with nearly vanishing internal flows. The anomalous viscosity-enhanced flow is caused by a viscosity-suppressed deformation of the droplet-air interface and a hydro- and aerodynamic coupling between the droplet and the air trapped within the micro/nanostructures (plastron). Our work demonstrates the unexpected role of the plastron in controlling fluid flow beyond the mere reduction in contact area and friction.