De novo DNA-based catch bonds.

All primary chemical interactions weaken under mechanical stress, which imposes fundamental mechanical limits on the materials constructed from them. Biological materials combine plasticity with strength, for which nature has evolved a unique solution-catch bonds, supramolecular interactions that strengthen under tension. Biological catch bonds use force-gated conformational switches to convert weak bonds into strong ones. So far, catch bonds remain exclusive to nature, leaving their potential as mechanoadaptive elements in synthetic systems untapped. Here we report the design and realization of artificial catch bonds. Starting from a minimal set of thermodynamic design requirements, we created a molecular motif capable of catch bonding. It consists of a DNA duplex featuring a cryptic domain that unfolds under tension to strengthen the interaction. We show that these catch bonds recreate force-enhanced rolling adhesion, a hallmark feature of biological catch bonds in bacteria and leukocytes. This Article introduces catch bonds into the synthetic domain, and could lead to the creation of artificial catch-bonded materials.

Moderated ionic bonding for water-free recyclable polyelectrolyte complex materials.

While nature extensively uses electrostatic bonding between oppositely charged polymers to assemble and stabilize materials, harnessing these interactions in synthetic systems has been challenging. Synthetic materials cross-linked with a high density of ionic bonds, such as polyelectrolyte complexes, only function properly when their charge interactions are attenuated in the presence of ample amounts of water; dehydrating these materials creates such strong Coulombic bonding that they become brittle, non-thermoplastic, and virtually impossible to process. We present a strategy to intrinsically moderate the electrostatic bond strengths in apolar polymeric solids by the covalent grafting of attenuator spacers to the charge carrying moieties. This produces a class of polyelectrolyte materials that have a charge density of 100%, are processable and malleable without requiring water, are highly solvent- and water-resistant, and are fully recyclable. These materials, which we coin "compleximers," marry the properties of thermoplastics and thermosets using tailored ionic bonding alone.

Evaporation-Induced Polyelectrolyte Complexation: The Role of Base Volatility and Cosolvents.

Film formation is a vital step for coating applications where a homogeneous, defect-free solid phase should be obtained, starting from a liquid casting formulation. Recently, an alternative waterborne-coating approach was proposed, based on the formation of a polyelectrolyte complex film. In this approach, an evaporating base induces a pH change during drying that initiates the complexation of oppositely charged polyelectrolytes, followed by further densification. In previous studies, ammonia was used as the evaporative base, leading to relatively fast evaporation and resulting in films showing significant brittleness, which tended to crack at low relative humidity or larger thicknesses. We hypothesize that slower complexation and/or evaporation can reduce the problematic stress build-up in the prepared polyelectrolyte complex coatings. For this reason, we studied the changes in the film formation process when there are different bases and cosolvents. We found that reducing the evaporation rate by changing ammonia to the slower evaporating dimethylamine or by adding DMSO as a cosolvent, led to less internal stress build-up during film formation, which could be beneficial for film application. Indeed, films prepared with ammonia showed cracking after 1 h, while films prepared with dimethylamine only showed cracking after one month. The fast evaporation of ammonia was also found to cause a temporary turbid phase, indicating phase separation, while for the slower evaporating bases, this did not occur. All prepared films remained sensitive to humidity, which poses the next challenge for these promising coatings.

Quantitative imaging methods for heterogeneous multi-component films.

The drying of multi-component dispersions is a common phenomenon in a variety of everyday applications, including coatings, inks, processed foods, and cosmetics. As the solvent evaporates, the different components may spontaneously segregate laterally and/or in depth, which can significantly impact the macroscopic properties of the dried film. To obtain a quantitative understanding of these processes, high-resolution analysis of segregation patterns is crucial. Yet, current state-of-the-art methods are limited to transparent, non-deformable labeled colloids, limiting their applicability. In this study, we employ three techniques that do not require customized samples, as their imaging contrast relies on intrinsic variations in the chemical nature of the constituent species: confocal Raman microscopy, cross-sectional Raman microscopy, and a combination of scanning electron microscopy and energy dispersive X-ray analysis (SEM-EDX). For broad accessibility, we offer a thorough guide to our experimental steps and data analysis methods. We benchmark the capabilities on a film that dries homogeneously at room temperature but exhibits distinct segregation features at elevated temperature, notably self-stratification, i.e., autonomous layer formation, due to a colloidal size mismatch. Confocal Raman microscopy offers a direct means to visualize structures in three dimensions without pre-treatment, its accuracy diminishes deeper within the film, making cross-sectional Raman imaging and SEM-EDX better options. The latter is the most elaborate method, yet we show that it can reveal the most subtle and small-scale microseparation of the two components in the lateral direction. This comparative study assists researchers in choosing and applying the most suitable technique to quantify structure formation in dried multi-component films.

3D printable soft and solvent-free thermoplastic elastomer containing dangling bottlebrush chains.

Polymer networks containing bottlebrush chains are emerging materials with exceptionally soft and highly tunable mechanical properties. However, such materials have not been extensively implemented in functional processing techniques such as three-dimensional (3D) printing. Here, we introduce a new design of soft and solvent-free polydimethylsiloxane (PDMS)-based thermoplastic elastomer which contains dangling and space-filling bottlebrush chains, featuring a yield stress and a rapid recovery after stress removal; both required for high spatial fidelity 3D printing. The developed material is composed of two copolymers; the main building block is a diblock copolymer with linear polystyrene (PS) block and bottlebrush PDMS block (PS-b-bbPDMS) while the second component is PS-b-PDMS-b-PS triblock, self-assembling to a physical network. This design provides independent tunability of each structural parameter on the molecular level, hence, macroscopic control of the materials' mechanical properties. Multiple self-supportive 3D structures with spanning elements are 3D printed at elevated temperatures using a developed material with a low shear modulus of G' = 3.3 kPa containing 3 : 1 molar ratio of diblock to triblock copolymers without the need for volatile solvent, or post-treatment. This 3D printing compatible design opens new opportunities to utilize the distinctive mechanical properties of bottlebrush materials for applications such as soft tissue scaffolds, sensors, actuators, and soft robots.

Elongated particles discharged with a conveyor belt in a two-dimensional silo.

The flow of elliptical particles out of a two-dimensional silo when extracted with a conveyor belt is analyzed experimentally. The conveyor belt-placed directly below the silo outlet-reduces the flow rate, increases the size of the stagnant zone, and it has a very strong influence on the relative velocity fluctuations as they strongly increase everywhere in the silo with decreasing belt speed. In other words, instead of slower but smooth flow, flow reduction by belt leads to intermittent flow. Interestingly, we show that this intermittency correlates with a strong reduction of the orientational order of the particles at the orifice region. Moreover, we observe that the average orientation of the grains passing through the outlet is modified when they are extracted with the belt, a feature that becomes more evident for large orifices.

Spatially heterogenous dynamics in colloidal gels during syneresis.

Syneresis, the compaction of a material accompanied by fluid expulsion, is a typical mechanical instability which exists among colloidal gel based materials and that negatively affects the quality of relevant applications. We shed light onto the internal dynamics of model colloidal gels undergoing syneresis using Laser Speckle Imaging (LSI). The resulting dynamical maps capture the distinct differences in spatial and temporal relaxation patterns between colloidal gels comprising solid and liquid particles. This indicates different mechanisms of syneresis between the two systems and highlights the importance of the constituent particles and their mobile or restrictive interfaces in the mechanical relaxation of the colloidal gels during syneresis.

Cross-linker Mobility Governs Fracture Behavior of Catch-Bonded Networks.

While most chemical bonds weaken under the action of mechanical force (called slip bond behavior), nature has developed bonds that do the opposite: their lifetime increases as force is applied. While such catch bonds have been studied quite extensively at the single molecule level and in adhesive contacts, recent work has shown that they are also abundantly present as crosslinkers in the actin cytoskeleton. However, their role and the mechanism by which they operate in these networks have remained unclear. Here, we present computer simulations that show how polymer networks crosslinked with either slip or catch bonds respond to mechanical stress. Our results reveal that catch bonding may be required to protect dynamic networks against fracture, in particular for mobile linkers that can diffuse freely after unbinding. While mobile slip bonds lead to networks that are very weak at high stresses, mobile catch bonds accumulate in high stress regions and thereby stabilize cracks, leading to a more ductile fracture behavior. This allows cells to combine structural adaptivity at low stresses with mechanical stability at high stresses.

Active microrheology of protein condensates using colloidal probe-AFM.

Protein condensates resulting from liquid-liquid phase separation have long been studied as bio-adhesives and coating materials for various applications. More recently, they are also being scrutinized as models for membraneless organelles in cells. Quantifying their interfacial mechanics and rheology at micrometer scales is vital for better understanding the physics underlying membraneless organelles in cells and for developing and improving technological applications of protein condensates. This study demonstrates how colloidal probe atomic force microscopy with an oscillating tip can be used to simultaneously investigate the interfacial mechanics and dynamic rheological properties of micro-scale protein condensates, formed via carefully controlled capillary condensation. This new approach can access oscillation frequencies ranging from 1 to 104 rad/s. By analyzing the data using an equivalent mechanical model, three characteristic frequency domains for the mechanics of micro-scale protein condensates are found: an interfacial tension-dominated domain at low frequencies, a transition domain (viscous-to-elastic crossover) at intermediate frequencies, and an elasticity-dominated domain at high frequencies, covering a broad range of time scales relevant in biology and technological applications of protein condensates.

In-situ and quantitative imaging of evaporation-induced stratification in binary suspensions.

The drying of a multi-component dispersion, such as water-based paint, ink and sunscreen to form a solid film, is a widespread process. Binary colloidal suspensions have proven capable of spontaneous layer formation through size segregation during drying. To design bespoke stratification patterns, a deeper understanding of how these emerge is crucial. Here, we visualize and quantify the spatiotemporally evolving concentration profiles in situ and with high resolution using confocal fluorescence microscopy of custom-designed binary dispersions in a well-defined geometry. Our results conclusively establish two distinct stratification routes, which give rise to three layered structures. A first thin layer develops directly underneath the evaporation front in which large particles are kinetically trapped. At later times, asymmetrical particle interactions lead to the formation of two subsequent layers enriched in small and large particles, respectively. The spatial extent and magnitude of demixing strongly depend on the initial volume fraction. We explain and reproduce the experimental concentration profiles using a theoretical model based on dynamic arrest and higher-order thermodynamic and hydrodynamic interactions. These insights unravel the key mechanisms underlying colloidal auto-stratification in multi-component suspensions, and allow preprogramming of stratification patterns in single-deposition formulations for future applications.

Synthesis of well-defined linear-bottlebrush-linear triblock copolymer towards architecturally-tunable soft materials.

Linear-bottlebrush-linear (LBBL) triblock copolymers are emerging systems for topologically-tunable elastic materials. In this paper, a new synthetic methodology is presented to synthesize LBBL polystyrene-block-bottlebrushpolydimethylsiloxane-block-polystyrene (PS-b-bbPDMS-b-PS) triblock copolymer via the "grafting onto" approach where the precursors are individually synthesized through living anionic polymerization and selective coupling reaction. In this two-step approach, polystyrene-block-polymethylvinylsiloxane (PS-b-PMVS) diblock copolymer with a low dispersity couples with another living PS block to form PS-b-PMVS-b-PS triblock copolymer. Secondly, this is followed by grafting of separately prepared monohydride-terminated PDMS chains with controllable grafting density through a hydrosilylation reaction. In addition to fully tunable architectural parameters, this approach permits a quantitative determination of the ratio of diblock and triblock bottlebrush copolymers and consistency between batches, highlighting the feasibility for scaled-up production. These LBBL triblock copolymers self-assemble into soft, low-modulus thermoplastic elastomers, and the precise knowledge of the composition is crucial for correlating microstructure to mechanical properties.

Force Transmission in Disordered Fibre Networks.

Cells residing in living tissues apply forces to their immediate surroundings to promote the restructuration of the extracellular matrix fibres and to transmit mechanical signals to other cells. Here we use a minimalist model to study how these forces, applied locally by cell contraction, propagate through the fibrous network in the extracellular matrix. In particular, we characterize how the transmission of forces is influenced by the connectivity of the network and by the bending rigidity of the fibers. For highly connected fiber networks the stresses spread out isotropically around the cell over a distance that first increases with increasing contraction of the cell and then saturates at a characteristic length. For lower connectivity, however, the stress pattern is highly asymmetric and is characterised by force chains that can transmit stresses over very long distances. We hope that our analysis of force transmission in fibrous networks can provide a new avenue for future studies on how the mechanical feedback between the cell and the ECM is coupled with the microscopic environment around the cells.

An actin mechanostat ensures hyphal tip sharpness in Phytophthora infestans to achieve host penetration.

Filamentous plant pathogens apply mechanical forces to pierce their hosts surface and penetrate its tissues. Devastating Phytophthora pathogens harness a specialized form of invasive tip growth to slice through the plant surface, wielding their hypha as a microscopic knife. Slicing requires a sharp hyphal tip that is not blunted at the site of the mechanical interaction. How tip shape is controlled, however, is unknown. We uncover an actin-based mechanostat in Phytophthora infestans that controls tip sharpness during penetration. Mechanical stimulation of the hypha leads to the emergence of an aster-like actin configuration, which shows fast, local, and quantitative feedback to the local stress. We evidence that this functions as an adaptive mechanical scaffold that sharpens the invasive weapon and prevents it from blunting. The hyphal tip mechanostat enables the efficient conversion of turgor into localized invasive pressures that are required to achieve host penetration.

Stretchy and disordered: Toward understanding fracture in soft network materials via mesoscopic computer simulations.

Soft network materials exist in numerous forms ranging from polymer networks, such as elastomers, to fiber networks, such as collagen. In addition, in colloidal gels, an underlying network structure can be identified, and several metamaterials and textiles can be considered network materials as well. Many of these materials share a highly disordered microstructure and can undergo large deformations before damage becomes visible at the macroscopic level. Despite their widespread presence, we still lack a clear picture of how the network structure controls the fracture processes of these soft materials. In this Perspective, we will focus on progress and open questions concerning fracture at the mesoscopic scale, in which the network architecture is clearly resolved, but neither the material-specific atomistic features nor the macroscopic sample geometries are considered. We will describe concepts regarding the network elastic response that have been established in recent years and turn out to be pre-requisites to understand the fracture response. We will mostly consider simulation studies, where the influence of specific network features on the material mechanics can be cleanly assessed. Rather than focusing on specific systems, we will discuss future challenges that should be addressed to gain new fundamental insights that would be relevant across several examples of soft network materials.

Large Scale Hydrodynamically Coupled Brownian Dynamics Simulations of Polymer Solutions Flowing through Porous Media.

Large scale simulations of polymer flow through porous media provide an important tool for solving problems in enhanced oil recovery, polymer processing and biological applications. In order to include the effects of a wide range of velocity and density fluctuations, we base our work on a coarse-grain particle-based model consisting of polymers following Brownian dynamics coupled to a background fluid flow through momentum conserving interactions. The polymers are represented as Finitely Extensible Non-Linear Elastic (FENE) dumbbells with interactions including slowly decaying transient forces to properly describe dynamic effects of the eliminated degrees of freedom. Model porous media are constructed from arrays of parallel solid beams with circular or square cross-sections, arranged periodically in the plane perpendicular to their axis. No-slip boundary conditions at the solid-fluid interfaces are imposed through interactions with artificial particles embedded within the solid part of the system. We compare the results of our simulations with those of standard Smoothed Particle Hydrodynamics simulations for Newtonian flow through the same porous media. We observe that in all cases the concentration of polymers at steady state is not uniform even though we start the simulations with a uniform polymer concentration, which is indicative of shear-induced cross-flow migration. Furthermore, we see the characteristic flattening of the velocity profile experimentally observed for shear-thinning polymer solutions flowing through channels as opposed to the parabolic Poiseuille flow profile for Newtonian fluids.

Sharing the Load: Stress Redistribution Governs Fracture of Polymer Double Networks.

The stress response of polymer double networks depends not only on the properties of the constituent networks but also on the interactions arising between them. Here, we demonstrate, via coarse-grained simulations, that both their global stress response and their microscopic fracture mechanics are governed by load sharing through these internetwork interactions. By comparing our results with affine predictions, where stress redistribution is by definition homogeneous, we show that stress redistribution is highly inhomogeneous. In particular, the affine prediction overestimates the fraction of broken chains by almost an order of magnitude. Furthermore, homogeneous stress distribution predicts a single fracture process, while in our simulations, fracture of sacrificial chains takes place in two steps governed by load sharing within a network and between networks, respectively. Our results thus provide a detailed microscopic picture of how inhomogeneous stress redistribution after rupture of chains governs the fracture of polymer double networks.

A slicing mechanism facilitates host entry by plant-pathogenic Phytophthora.

Phytophthora species, classified as oomycetes, are among the most destructive plant pathogens worldwide and pose a substantial threat to food security. Plant pathogens have developed various methods to breach the cuticle and walls of plant cells. For example, plant-pathogenic fungi use a 'brute-force' approach by producing a specialized and fortified invasion organ to generate invasive pressures. Unlike in fungi, the biomechanics of host invasion in oomycetes remains poorly understood. Here, using a combination of surface-deformation imaging, molecular-fracture sensors and modelling, we find that Phytophthora infestans, Phytophthora palmivora and Phytophthora capsici slice through the plant surface to gain entry into host tissues. To distinguish this mode of entry from the brute-force approach of fungi that use appressoria, we name this oomycete entry without appressorium formation 'naifu' invasion. Naifu invasion relies on polarized, non-concentric, force generation onto the surface at an oblique angle, which concentrates stresses at the site of invasion to enable surface breaching. Measurements of surface deformations during invasion of artificial substrates reveal a polarized mechanical geometry that we describe using a mathematical model. We confirm that the same mode of entry is used on real hosts. Naifu invasion uses actin-mediated polarity, surface adherence and turgor generation to enable Phytophthora to invade hosts without requiring specialized organs or vast turgor generation.

Core-Shell Microcapsules from Unpurified Legume Flours.

Plant-based ingredients are key building blocks for future sustainable advanced materials. Functionality is typically higher for highly purified plant-based ingredients, but this is at the expense of their sustainability value. Here, a method is introduced for creating a soft functional material, with structural elements ranging from the nanometer to the millimeter scale, directly from legume flours. Globulins from soy and pea flours are extracted in their native state at acidic pH and mixed with gum arabic, resulting in liquid-liquid phase separation into a dilute phase and a viscoelastic complex coacervate. Interfacial tensions of the coacervates, determined via AFM-based probing of capillary condensation, are found to be very low (γ = 48.5 and 32.3 µN/m for, respectively, soy and pea), thus promoting the deposition of a shell of coacervate material around oil droplets. Despite the complex nature of the starting material, the dependence of interfacial tensions on salt concentrations follows a scaling law previously shown to hold for model complex coacervates. Curing of the coacervate material into a strong and purely elastic hydrogel is shown to be possible via simple heating, both in bulk and as a shell around oil droplets, thus providing proof of principle for the fabrication of precise core-shell microcapsules directly from legume flours.

Single-Step Application of Polyelectrolyte Complex Films as Oxygen Barrier Coatings.

Polyelectrolyte complex (PEC) films such as polyelectrolyte multilayers have demonstrated excellent oxygen barrier properties, but unfortunately, the established layer-by-layer approaches are laborious and difficult to scale up. Here, we demonstrate a novel single-step approach to produce a PEC film, based on the use of a volatile base. Ammonia was used to adjust the pH of poly(acrylic acid) (PAA) so that direct complexation was avoided when it was mixed with polyethylenimine (PEI). Different charge ratios of homogeneous PEI/PAA solutions were successfully prepared and phase diagrams varying the concentration of ammonia or polyelectrolyte were made to study the phase behavior of PEI, PAA, and ammonia in water. Transparent ∼1 µm thick films were successfully deposited on biaxially orientated polypropylene (BOPP) sheets using a Meyer rod. After casting the films, the decrease in pH, caused by the evaporation of ammonia, triggered the complexation during drying. The oxygen permeation properties of films with different ratios and single polyelectrolytes were tested. All films displayed excellent oxygen barrier properties, with an oxygen permeation below 4 cm3·m-2·day-1·atm-1 (<0.002 barrer) at the optimum ratio of 2:1 PEI/PAA. This ammonia evaporation-induced complexation approach creates a new pathway to prepare PEC films in one simple step while allowing the possibility of recycling.

Long-term single-cell imaging and simulations of microtubules reveal principles behind wall patterning during proto-xylem development.

Plants are the tallest organisms on Earth; a feature sustained by solute-transporting xylem vessels in the plant vasculature. The xylem vessels are supported by strong cell walls that are assembled in intricate patterns. Cortical microtubules direct wall deposition and need to rapidly re-organize during xylem cell development. Here, we establish long-term live-cell imaging of single Arabidopsis cells undergoing proto-xylem trans-differentiation, resulting in spiral wall patterns, to understand microtubule re-organization. We find that the re-organization requires local microtubule de-stabilization in band-interspersing gaps. Using microtubule simulations, we recapitulate the process in silico and predict that spatio-temporal control of microtubule nucleation is critical for pattern formation, which we confirm in vivo. By combining simulations and live-cell imaging we further explain how the xylem wall-deficient and microtubule-severing KATANIN contributes to microtubule and wall patterning. Hence, by combining quantitative microscopy and modelling we devise a framework to understand how microtubule re-organization supports wall patterning.