Liquid Metal-Mediated Mechanochemical Polymerization.

Mechanically controlled polymerization that employs the mechanical energy to fabricate novel synthetic materials has attracted considerable interest. However, only a few examples have been achieved so far, owing to the limited choices of materials and strategies. Herein, a versatile, liquid metal (LM)-mediated mechanochemical polymerization method (LMMMP) is developed for the air-compatible, robust preparation of polymers in an aqueous solution. This method involves the simultaneous disruption of bulk LMs into micro- and nanodroplets and the combination of monomers into polymers during ultrasonic irradiation. The pristine and reactive LM surface continuously generated by ultrasound endows this polymerization method with excellent oxygen tolerance, high reaction rate, and the ability to produce polymers with high molecular weight from a wide variety of water-soluble monomers. Besides, LM droplets are readily reclaimed and reused for polymerization. The authors envision that the LMMMP promotes the utilization of mechanical energy for the synthesis of functional polymers, constitutes a novel fabrication approach for polymer-LM nanocomposites, and provides new insight into the design of LM-based platforms for polymerization.

Softening and Shape Morphing of Stiff Tough Hydrogels by Localized Unlocking of the Trivalent Ionically Cross-Linked Centers.

The mechanical properties (e.g., stiffness, stretchability) of prefabricated hydrogels are of pivotal importance for diverse applications in tissue engineering, soft robotics, and medicine. This study reports a feasible method to fabricate ultrasoft and highly stretchable structures from stiff and tough hydrogels of low stretchability and the application of these switchable hydrogels in programmable shape-morphing systems. Stiff and tough hydrogel structures are first fabricated by the mechanical strengthening of Ca2+ -alginate/polyacrylamide tough hydrogels by addition of Fe3+ ions, which introduces Fe3+ ionically cross-linked centers into the Ca2+ divalent cross-linked hydrogel, forming an additional and much less flexible trivalent ionically cross-linked network. The resulting stiff and tough hydrogels are exposed to an L-ascorbic acid (vitamin C, VC) solution to rapidly reduce Fe3+ to Fe2+ . As a result, flexible divalent ionically cross-linked networks are formed, leading to swift softening of the stiff and tough hydrogels. Moreover, localized stiffness variation of the tough hydrogels can be realized by precise patterning of the VC solution. To validate this concept, sequential steps of VC patterning are carried out for local tuning of the stiffness of the hydrogels. With this strategy, localized softening, unfolding, and sequential folding of the tough hydrogels into complex 3D structures is demonstrated.

Enzyme degradable polymersomes from hyaluronic acid-block-poly(ε-caprolactone) copolymers for the detection of enzymes of pathogenic bacteria.

We introduce a new hyaluronidase-responsive amphiphilic block copolymer system, based on hyaluronic acid (HYA) and polycaprolactone (PCL), that can be assembled into polymersomes by an inversed solvent shift method. By exploiting the triggered release of encapsulated dye molecules, these HYA-block-PCL polymersomes lend themselves as an autonomous sensing system for the detection of the presence of hyaluronidase, which is produced among others by the pathogenic bacterium Staphylococcus aureus. The synthesis of the enzyme-responsive HYA-block-PCL block copolymers was carried out by copper-catalyzed Huisgen 1,3-dipolar cycloaddition of ω-azide-terminated PCL and ω-alkyne-functionalized HYA. The structure of the HYA-block-PCL assemblies and their enzyme-triggered degradation and concomitant cargo release were investigated by dynamic light scattering, fluorescence spectroscopy, confocal laser-scanning microscopy, scanning and transmission electron, and atomic force microscopy. As shown, a wide range of reporter dye molecules as well as antimicrobials can be encapsulated into the vesicles during formation and are released upon the addition of hyaluronidase.

Controlled surface chemistry of diamond/ß-SiC composite films for preferential protein adsorption.

Diamond and SiC both process extraordinary biocompatible, electronic, and chemical properties. A combination of diamond and SiC may lead to highly stable materials, e.g., for implants or biosensors with excellent sensing properties. Here we report on the controllable surface chemistry of diamond/ß-SiC composite films and its effect on protein adsorption. For systematic and high-throughput investigations, novel diamond/ß-SiC composite films with gradient composition have been synthesized using the hot filament chemical vapor deposition (HFCVD) technique. As revealed by scanning electron microscopy (SEM), the diamond/ß-SiC ratio of the composite films shows a continuous change from pure diamond to ß-SiC over a length of ∼ 10 mm on the surface. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) was employed to unveil the surface termination of chemically oxidized and hydrogen treated surfaces. The surface chemistry of the composite films was found to depend on diamond/ß-SiC ratio and the surface treatment. As observed by confocal fluorescence microscopy, albumin and fibrinogen were preferentially adsorbed from buffer: after surface oxidation, the proteins preferred to adsorb on diamond rather than on ß-SiC, resulting in an increasing amount of proteins adsorbed to the gradient surfaces with increasing diamond/ß-SiC ratio. By contrast, for hydrogen-treated surfaces, the proteins preferentially adsorbed on ß-SiC, leading to a decreasing amount of albumin adsorbed on the gradient surfaces with increasing diamond/ß-SiC ratio. The mechanism of preferential protein adsorption is discussed by considering the hydrogen bonding of the water self-association network to OH-terminated surfaces and the change of the polar surface energy component, which was determined according to the van Oss method. These results suggest that the diamond/ß-SiC gradient film can be a promising material for biomedical applications which require good biocompatibility and selective adsorption of proteins and cells to direct cell migration.

Biomimetic anti-freezing polymeric hydrogels: keeping soft-wet materials active in cold environments.

As one of the most outstanding materials, the analysis of the structure and function of hydrogels has been extensively carried out to tailor and adapt them to various fields of application. The high water content, which is beneficial for plenty of applications in the biomedical setting, prevents the adoption of hydrogels in flexible electronics and sensors in real life applications, because hydrogels lose their excellent properties, including conductivity, transparency, flexibility, etc., upon freezing at sub-zero temperatures. Therefore, depressing the liquid-solid phase transition temperature is a powerful means to expand the application scope of hydrogels, and will benefit the chemical engineering and materials science communities. This review summarizes the recent research progress of anti-freezing hydrogels. At first, approaches for the generation of anti-freezing (hydro)gels are introduced and their anti-freezing mechanisms and performances are briefly discussed. These approaches are either based on addition of salts, alcohols (cryoprotectants and organohydrogels), and ionic liquids (ionogels), modification of the polymer network or a combination of several techniques. Then, a concise overview of applications leveraged by the widened temperature resistance is provided and future research areas and developments are envisaged.

Giant Biodegradable Poly(ethylene glycol)-block-Poly(ε-caprolactone) Polymersomes by Electroformation.

Here, the formation of giant enzyme-degradable polymersomes using the electroformation method is reported. Poly(ethylene glycol)-block-poly(ε-caprolactone) polymersomes have been shown previously to be attractive candidates for the detection of bacterial proteases and protease mediated release of encapsulated reporter dyes and antimicrobials. To maximize the efficiency, the maximization of block copolymer (BCP) vesicle size without compromising their properties is of prime importance. Thus, the physical-chemical properties of the BCP necessary to self-assemble into polymeric vesicles by electroformation are first identified. Subsequently, the morphology of the self-assembled structures is extensively characterized by different microscopy techniques. The vesicular structures are visualized for giant polymersomes by confocal laser scanning microscopy upon incorporation of reporter dyes during the self-assembly process. Using time correlated single photon counting and by analyzing the fluorescence decay curves, the nanoenvironment of the encapsulated fluorophores is unveiled. Using this approach, the hollow core structure of the polymersomes is confirmed. Finally, the encapsulation of different dyes added during the electroformation process is studied. The results underline the potential of this approach for obtaining microcapsules for subsequent triggered release of signaling fluorophores or antimicrobially active cargo molecules that can be used for bacterial infection diagnostics and/or treatment.

Robust Biomimetic Hierarchical Diamond Architecture with a Self-Cleaning, Antibacterial, and Antibiofouling Surface.

Biofouling is a worldwide problem from healthcare to marine exploration. Aggressive biofouling, wear, and corrosion lead to severe deterioration in function and durability. Here, micro- and nanostructured hierarchical diamond films mimicking the morphology of plant leaves were developed to simultaneously achieve superhydrophobicity, antibacterial efficacy, and marine antibiofouling, combined with mechanical and chemical robustness. These coatings were designed and successfully constructed on various commercial substrates, such as titanium alloys, silicon, and quartz glass via a chemical vapor deposition process. The unique surface structure of diamond films reduced bacteria attachment by 90-99%. In the marine environment, these biomimetic diamond films significantly reduced more than 95% adhesion of green algae. The structured diamond films retained mechanical robustness, superhydrophobicity, and antibacterial efficacy under high abrasion and corrosive conditions, exhibiting at least 20 times enhanced wear resistance than the bare commercial substrates even after long-term immersion in seawater.