Bioinspired Metal-Ligand Networks with Enhanced Stability and Performance: Facile Preparation of Hydroxypyridinone (HOPO)-Functionalized Materials.

Bioinspired hydroxypyridinone (HOPO)functionalized materials are shown to display a remarkable capacity for stability and for chelating a wide array of metal ions. This allows for the synthesis of multifunctional networks with diverse physical properties when compared to traditional catechol systems. In the present study, we report a facile, one-pot synthesis of an amino HOPO ligand and simple, scalable incorporation into PEG-acrylate based networks via active ester chemistry.

A colloidal model for the equilibrium assembly and liquid-liquid phase separation of the reflectin A1 protein.

Reflectin is an intrinsically disordered protein known for its ability to modulate the biophotonic camouflage of cephalopods based on its assembly-induced osmotic properties. Its reversible self-assembly into discrete, size-controlled clusters and condensed droplets are known to depend sensitively on the net protein charge, making reflectin stimuli-responsive to pH, phosphorylation, and electric fields. Despite considerable efforts to characterize this behavior, the detailed physical mechanisms of reflectin's assembly are not yet fully understood.

Experimental observation of near-wall effects during the puncture of soft solids.

Performing conventional mechanical characterization techniques on soft materials can be challenging due to issues such as limited sample volumes and clamping difficulties. Deep indentation and puncture is a promising alternative as it is an information-rich measurement with the potential to be performed in a high-throughput manner. Despite its promise, the method lacks standardized protocols, and open questions remain about its possible limitations.

Dynamic Manipulation of Droplets on Liquid-Infused Surfaces Using Photoresponsive Surfactant.

Fast and programmable transport of droplets on a substrate is desirable in microfluidic, thermal, biomedical, and energy devices. Photoresponsive surfactants are promising candidates to manipulate droplet motion due to their ability to modify interfacial tension and generate "photo-Marangoni" flow under light stimuli. Previous works have demonstrated photo-Marangoni droplet migration in liquid media; however, migration on other substrates, including solid and liquid-infused surfaces (LIS), remains an outstanding challenge.

Coacervate or precipitate? Formation of non-equilibrium microstructures in coacervate emulsions.

Non-equilibrium processing of aqueous polyelectrolyte complex (PEC) coacervates is critical to many applications. In particular, many coacervate-forming systems are known to become trapped in out-of-equilibrium states (, precipitation). The mechanism and conditions under which these states form, and whether they age, is not clearly understood.

Lithium isotopes differentially modify mitochondrial amorphous calcium phosphate cluster size distribution and calcium capacity.

Lithium is commonly prescribed as a mood stabilizer in a variety of mental health conditions, yet its molecular mode of action is incompletely understood. Many cellular events associated with lithium appear tied to mitochondrial function. Further, recent evidence suggests that lithium bioactivities are isotope specific.

Designing Superlubricious Hydrogels from Spontaneous Peroxidation Gradients.

Hydrogels are hydrated three-dimensional networks of hydrophilic polymers that are commonly used in the biomedical industry due to their mechanical and structural tunability, biocompatibility, and similar water content to biological tissues. The surface structure of hydrogels polymerized through free-radical polymerization can be modified by controlling environmental oxygen concentrations, leading to the formation of a polymer concentration gradient. In this work, 17.

Competition between β-Sheet and Coacervate Domains Yields Diverse Morphologies in Mixtures of Oppositely Charged Homochiral Polypeptides.

Biomolecular assembly processes involving competition between specific intermolecular interactions and thermodynamic phase instability have been implicated in a number of pathological states and technological applications of biomaterials. As a model for such processes, aqueous mixtures of oppositely charged homochiral polypeptides such as poly-l-lysine and poly-l-glutamic acid have been reported to form either β-sheet-rich solid-like precipitates or liquid-like coacervate droplets depending on competing hydrogen bonding interactions. Herein, we report studies of polypeptide mixtures that reveal unexpectedly diverse morphologies ranging from partially coalescing and aggregated droplets to bulk precipitates, as well as a previously unreported re-entrant liquid-liquid phase separation at high polypeptide concentration and ionic strength.

Tailoring Writability and Performance of Star Block Copolypeptides Hydrogels through Side-Chain Design.

Shear-recoverable hydrogels based on block copolypeptides with rapid self-recovery hold potential in extrudable and injectable 3D-printing applications. In this work, a series of 3-arm star-shaped block copolypeptides composed of an inner hydrophilic poly(l-glutamate) domain and an outer β-sheet forming domain is synthesized with varying side chains and block lengths. By changing the β-sheet forming domains, hydrogels with diverse microstructures and mechanical properties are prepared and structure-function relationships are determined using scattering and rheological techniques.

Molecular-scale substrate anisotropy, crowding and division drive collective behaviours in cell monolayers.

The ability of cells to reorganize in response to external stimuli is important in areas ranging from morphogenesis to tissue engineering. While nematic order is common in biological tissues, it typically only extends to small regions of cells interacting via steric repulsion. On isotropic substrates, elongated cells can co-align due to steric effects, forming ordered but randomly oriented finite-size domains.

Minimal conditions for solidification and thermal processing of colloidal gels.

Colloidal gelation is used to form processable soft solids from a wide range of functional materials. Although multiple gelation routes are known to create gels of different types, the microscopic processes during gelation that differentiate them remain murky. A fundamental question is how the thermodynamic quench influences the microscopic driving forces of gelation, and determines the threshold or minimal conditions where gels form.

Modular Synthesis and Patterning of High-Stiffness Networks by Postpolymerization Functionalization with Iron-Catechol Complexes.

Bioinspired iron-catechol cross-links have shown remarkable success in increasing the mechanical properties of polymer networks, in part due to clustering of Fe-catechol domains which act as secondary network reinforcing sites. We report a versatile synthetic procedure to prepare modular PEG-acrylate networks with independently tunable covalent bis(acrylate) and supramolecular Fe-catechol cross-linking. Initial control of network structure is achieved through radical polymerization and cross-linking, followed by postpolymerization incorporation of catechol units via quantitative active ester chemistry and subsequent complexation with iron salts.

Phosphates form spectroscopically dark state assemblies in common aqueous solutions.

Phosphates and polyphosphates play ubiquitous roles in biology as integral structural components of cell membranes and bone, or as vehicles of energy storage via adenosine triphosphate and phosphocreatine. The solution phase space of phosphate species appears more complex than previously known. We present nuclear magnetic resonance (NMR) and cryogenic transmission electron microscopy (cryo-TEM) experiments that suggest phosphate species including orthophosphates, pyrophosphates, and adenosine phosphates associate into dynamic assemblies in dilute solutions that are spectroscopically "dark.

Strength of fluid-filled soft composites across the elastofracture length.

Materials that utilize heterogeneous microstructures to control macroscopic mechanical response are ubiquitous in nature. Yet, translating nature's lessons to create synthetic soft solids has remained challenging. This is largely due to the limited synthetic routes available for creating soft composites, particularly with submicron features, as well as uncertainty surrounding the role of such a microstructured secondary phase in determining material behavior.

Modeling colloidal interactions that predict equilibrium and non-equilibrium states.

Modulating the interaction potential between colloids suspended in a fluid can trigger equilibrium phase transitions as well as the formation of non-equilibrium "arrested states," such as gels and glasses. Faithful representation of such interactions is essential for using simulation to interrogate the microscopic details of non-equilibrium behavior and for extrapolating observations to new regions of phase space that are difficult to explore in experiments. Although the extended law of corresponding states predicts equilibrium phases for systems with short-ranged interactions, it proves inadequate for equilibrium predictions of systems with longer-ranged interactions and for predicting non-equilibrium phenomena in systems with either short- or long-ranged interactions.

Rational mechanochemical design of Diels-Alder crosslinked biocompatible hydrogels with enhanced properties.

An important but often overlooked feature of Diels-Alder (DA) cycloadditions is the ability for DA adducts to undergo mechanically induced cycloreversion when placed under force. Herein, we demonstrate that the commonly employed DA cycloaddition between furan and maleimide to crosslink hydrogels results in slow gelation kinetics and "mechanolabile" crosslinks that relate to reduced material strength. Through rational computational design, "mechanoresistant" DA adducts were identified by constrained geometries simulate external force models and employed to enhance failure strength of crosslinked hydrogels.

High-throughput microscopy to determine morphology, microrheology, and phase boundaries applied to phase separating coacervates.

Evolution of composition, rheology, and morphology during phase separation in complex fluids is highly coupled to rheological and mass transport processes within the emerging phases, and understanding this coupling is critical for materials design of multiphase complex fluids. Characterizing these dependencies typically requires careful measurement of a large number of equilibrium and transport properties that are difficult to measure as phase separation proceeds. Here, we propose and demonstrate a high-throughput microscopy platform to achieve simultaneous, mapping of time-evolving morphology and microrheology in phase separating complex fluids over a large compositional space.

Depinning of Multiphase Fluid Using Light and Photo-Responsive Surfactants.

The development of noninvasive and robust strategies for manipulation of droplets and bubbles is crucial in applications such as boiling and condensation, electrocatalysis, and microfluidics. In this work, we realize the swift departure of droplets and bubbles from solid substrates by introducing photoresponsive surfactants and applying asymmetric illumination, thereby inducing a "photo-Marangoni" lift force. Experiments show that a pinned toluene droplet can depart the substrate in only 0.

Engineering Gelation Kinetics in Living Silk Hydrogels by Differential Dynamic Microscopy Microrheology and Machine Learning.

Microbes embedded in hydrogels comprise one form of living material. Discovering formulations that balance potentially competing for mechanical and biological properties in living hydrogels-for example, gel time of the hydrogel formulation and viability of the embedded organisms-can be challenging. In this study, a pipeline is developed to automate the characterization of the gel time of hydrogel formulations.

Uncertainty quantification and estimation in differential dynamic microscopy.

Differential dynamic microscopy (DDM) is a form of video image analysis that combines the sensitivity of scattering and the direct visualization benefits of microscopy. DDM is broadly useful in determining dynamical properties including the intermediate scattering function for many spatiotemporally correlated systems. Despite its straightforward analysis, DDM has not been fully adopted as a routine characterization tool, largely due to computational cost and lack of algorithmic robustness.

Influence of Polarity Change and Photophysical Effects on Photosurfactant-Driven Wetting.

Photosurfactants have shown considerable promise for enabling stimuli-responsive control of the properties and motion of fluid interfaces. Recently, a number of photoswitch chemistries have emerged to tailor the photoresponsive properties of photosurfactants. However, systematic studies investigating how photoresponsive surfactant behavior depends on the photochemical and photophysical properties of the switch remain scarce.

Flow-Induced Concentration Nonuniformity and Shear Banding in Entangled Polymer Solutions.

Recent models have predicted entangled polymer solutions could shear band due to unstable flow-induced demixing. This work provides the first experimental probe of the in situ concentration profile of entangled polymer solutions under shear. At shear rates above a critical value, we show that the concentration and velocity profiles can develop bands, in quantitative agreement with steady-state model predictions.

Design and characterization of a 3D-printed staggered herringbone mixer.

3D printing holds potential as a faster, cheaper alternative compared with traditional photolithography for the fabrication of microfluidic devices by replica molding. However, the influence of printing resolution and quality on device design and performance has yet to receive detailed study. Here, we investigate the use of 3D-printed molds to create staggered herringbone mixers (SHMs) with feature sizes ranging from ∼100 to 500 μm.

Hydrogen Bonding Strength Determines Water Diffusivity in Polymer Ionogels.

Polymeric ionogels, cross-linked gels swollen by ionic liquids (ILs), are useful vehicles for the release and storage of molecular solutes in separation, delivery, and other applications. Although rapid solute diffusion is often critical for performance, it remains challenging to predict diffusivities across multidimensional composition spaces. Recently, we showed that water (a neutral solute) diffuses through alkyl-methylimidazolium halide ILs by hopping between hydrogen bonding sites on relatively immobile cations.