Strain-stiffening is observed and characterized in flexible PEG hydrogel networks crosslinked via dynamic-covalent boronate ester bonds, revealing an uncommon synthetic mimic of a mechanoresponse found natural biopolymer networks.

Biology achieves remarkable function through processes arising from spontaneous or transient liquid–liquid phase separation (LLPS) of proteins and other biomolecules. While polymeric systems can achieve similar phenomena simple complex coacervation, LLPS with supramolecular materials has been less commonly shown. Functional applications for synthetic are an expanding area emphasis, particular focus on capturing the dynamic state these structures use in biomedicine. Here, a net-cationic...

The ongoing rise in diabetes incidence necessitates improved therapeutic strategies to enable precise blood glucose control with convenient device form factors. Microneedle patches are one such platform capable of achieving delivery through the skin. In recent years, polymeric microneedle arrays have been reported using methods situ polymerization and covalent crosslinking molds. spite promising results, carries a risk exposure toxic unreacted precursors remaining device. Here, patch is...

The transient self-assembly of molecules under the direction a consumable fuel source is fundamental to biological processes such as cellular organization and motility. Such biomolecular assemblies exist in an out-of-equilibrium state, requiring continuous consumption high energy molecules. At same time, creation bioinspired supramolecular hydrogels has traditionally focused on associations occurring at thermodynamic equilibrium state. Here, are prepared from cucurbit[7]uril host-guest...

Abstract Diabetes is one of the most pressing healthcare challenges facing society. Dysfunctional insulin signaling causes diabetes, leading to blood glucose instability and many associated complications. While administration exogenous then essential for achieving control, issues with dosing accuracy timing remain. Hydrogel‐based drug delivery systems have been broadly explored controlled protein release, including applications in long‐lasting oral delivery. More recently, efforts focused on...

Abstract Dynamic hydrogel crosslinking captures network reorganization and self‐healing of natural materials, yet is often accompanied by reduced mechanical properties compared to covalent analogs. Toughening possible in certain materials with processing directional freeze‐casting salting‐out, producing hierarchically organized networks directionally enhanced properties. The implications including dynamic supramolecular alongside such processes are unclear. Here, a prepared from homoternary...

Abstract Granular hydrogel scaffolds (GHS), composed of jammed microparticles (microgels), have emerged to overcome the structural limitations nonporous (bulk) hydrogels. Microscale void spaces among microgels in GHS promote cell infiltration and host tissue integration; however, prevalent use spherical limits fraction that random close packing. To address this persistent challenge, a new class gelatin methacryloyl (GelMA) comprising porous microgels, fabricated via thermally induced polymer...

Diabetes requires precise insulin management to maintain glycemic control and prevent severe complications. Glucose-responsive delivery systems envision an autonomous approach improve therapy. Here, a glucose-sensitive system comprising hyaluronic acid conjugated with diboronate glucose binder as carrier for diol-modified is shown. This seeks improved precision in delivery, leveraging bidentate binding achieve enhanced affinity specificity. Modification of diol motif preserves its native...

Stimuli-responsive hydrogels are an area of active discovery for approaches to deliver therapeutics in response disease-specific indicators. Glucose-responsive delivery insulin is particular interest better managing diabetes. Accordingly, have been explored as platforms that enable both a rate and dose release aligning with the real-time physiological disease state; materials often include glucose sensing by dynamic-covalent cross-linking between phenylboronic acids (PBAs) diols, competition...

Peptide self-assembly is a powerful tool to prepare functional materials at the nanoscale. Often, resulting have high aspect-ratio, with intermolecular β-sheet formation underlying 1D fibrillar structures. Inspired by dynamic structures in nature, peptide increasingly moving toward stimuli-responsive designs wherein assembled are formed, altered, or dissipated response specific cue. Here, bearing prosthetic glucose-binding phenylboronic acid (PBA) demonstrated self-assemble into an uncommon...

Abstract The management of diabetes in a manner offering autonomous insulin therapy responsive to glucose‐directed need, and moreover with dosing schedule amenable facile administration, remains an ongoing goal improve the standard care. While basal insulins reduced frequency, even once‐weekly are on horizon, there is still no approved that offers glucose‐responsive function. Herein, nanoscale complex combining both electrostatic‐ dynamic‐covalent interactions between synthetic dendrimer...

Point-of-use devices to conveniently deliver protein therapeutics are of growing need. Microneedles offer an approach biopharmaceuticals across the skin and circumvent syringe-based injection or harsh oral environments. Certain microneedles rapidly dissolve their payload, while others affix for sustained release. Here, a microneedle platform combining PEG-based supramolecular polymer network with mechanical biopolymer is able penetrate skin, where subsequently swell; those composed...

The formation of transient structures plays important roles in biological processes, capturing temporary states matter through influx energy or reaction networks catalyzed by enzymes. These natural inspire efforts to mimic this elegant mechanism structural control synthetic analogues. Specifically, though traditional supramolecular materials are designed on the basis equilibrium formation, recent have explored out-of-equilibrium these using both direct and indirect mechanisms; preponderance...

Abstract In an effort to augment the function of supramolecular biomaterials, recent efforts have explored creation hybrid materials that couple and covalent components. Here, benzenetricarboxamide (BTA) polymer motif is modified present a phenylboronic acid (PBA) in order promote crosslinking 1D BTA stacks by PBA–diol dynamic‐covalent bonds through addition multi‐arm diol‐bearing crosslinker. Interestingly, combination these two motifs serves frustrate resulting assembly process, yielding...

The atomic composition and chemical structure of polymers is fundamental to dictating properties applications.

We report a highly functionalized 2-pyranone small molecule prepared from tert-butyl diphenyl silyl ketene using an alkoxide catalyst and thermally induced rearrangement. Treatment of the with substoichiometric amount led to formation trimer which was isolated fully characterized; heating this in 1,4-dioxane solution thermal rearrangement, yielding product 2-pyranone. The intermediate are characterized by 1D 2D nuclear magnetic resonance (NMR) spectroscopies, mass spectrometry, single...

Abstract The transient self‐assembly of molecules under the direction a consumable fuel source is fundamental to biological processes such as cellular organization and motility. Such biomolecular assemblies exist in an out‐of‐equilibrium state, requiring continuous consumption high energy molecules. At same time, creation bioinspired supramolecular hydrogels has traditionally focused on associations occurring at thermodynamic equilibrium state. Here, are prepared from cucurbit[7]uril...

The management of diabetes in a manner offering autonomous insulin therapy responsive to glucose-directed need, and moreover with dosing schedule amenable facile administration, remains an ongoing goal improve the standard care. While basal insulins reduced frequency, even once-weekly are on horizon, there is still no approved that offers glucose-responsive function. Herein, nanoscale complex combining both electrostatic dynamic-covalent interactions between synthetic dendrimer carrier...

Silyl-substituted ketenes are attractive molecular building blocks due to their stability and ease of storage, as opposed unstable alkyl aryl ketenes. To better understand the reactivity silyl and, in turn, use preparation highly functionalized small molecules, reaction with different nucleophiles was studied. The addition alcohol, amine, or thiol central carbon ketene, followed by proton transfer afforded α-silyl ester, amide, thio-ester, respectively. Catalytic amounts Lewis acid greatly...