Creating Stiff,Tough, and Functional Hydrogel Composites with Low‐Melting‐Point Alloys

Reinforcing hydrogels with a rigid scaffold is a promising method to greatly expand the mechanical and physical properties of hydrogels. One of the challenges of creating hydrogel composites is the significant stress that occurs due to swelling mismatch between the water‐swollen hydrogel matrix and the rigid skeleton in aqueous media. This stress can cause physical deformation (wrinkling, buckling, or fracture), preventing the fabrication of robust composites. Here, a simple yet versatile method is introduced to create “macroscale” hydrogel composites, by utilizing a rigid reinforcing phase that can relieve stress‐induced deformation. A low‐melting‐point alloy that can transform from a load‐bearing solid state to a free‐deformable liquid state at relatively low temperature is used as a reinforcing skeleton, which enables the release of any swelling mismatch, regardless of the matrix swelling degree in liquid media. This design can generally provide hydrogels with hybridized functions, including excellent mechanical properties, shape memory, and thermal healing, which are often difficult or impossible to achieve with single‐component hydrogel systems. Furthermore, this technique enables controlled electrochemical reactions and channel‐structure templating in hydrogel matrices. This work may play an important role in the future design of soft robots, wearable electronics, and biocompatible functional materials.     

Colloid‐in‐Liquid Crystal Gels that Respond to Biomolecular Interactions

This paper advances the design of stimuli‐responsive materials based on colloidal particles dispersed in liquid crystals (LCs). Specifically, thin films of colloid‐in‐liquid crystal (CLC) gels undergo easily visualized ordering transitions in response to reversible and irreversible (enzymatic) biomolecular interactions occurring at the aqueous interfaces of the gels. In particular, LC ordering transitions can propagate across the entire thickness of the gels. However, confinement of the LC to small domains with lateral sizes of ～10 μm does change the nature of the anchoring transitions, as compared to films of pure LC, due to the effects of confinement on the elastic energy stored in the LC. The effects of confinement are also observed to cause the response of individual domains of the LC within the CLC gel to vary significantly from one to another, indicating that manipulation of LC domain size and shape can provide the basis of a general and facile method to tune the response of these LC‐based physical gels to interfacial phenomena. Overall, the results presented in this paper establish that CLC gels offer a promising approach to the preparation of self‐supporting, LC‐based stimuli‐responsive materials.     

Cover Picture: Self‐Assembled Metal Oxide Bilayer Films with “Single‐Crystalline” Overlayer Mesopore Structure (Adv. Mater. 8/2007)

Mesoporous films with biaxial, “single‐crystalline” arrangements of spherical pores are obtained by “evaporation‐induced self‐assembly” (EISA) in work reported by Torsten Brezesinski, Markus Antonietti, and Bernd Smarsly on p. 1074. The films are dip‐coated onto a sublayer with sufficiently different surface tension and a specific nanoscale periodicity. Low adhesion to the sublayer surface results in a relatively small number of nucleation sites and a uniform orientation of the evolving mesostructure in the toplayer.     

Controlled Fabrication of Micropatterned Supramolecular Gels by Directed Self‐Assembly of Small Molecular Gelators

Herein, the micropatterning of supramolecular gels with oriented growth direction and controllable spatial dimensions by directing the self‐assembly of small molecular gelators is reported. This process is associated with an acid‐catalyzed formation of gelators from two soluble precursor molecules. To control the localized formation and self‐assembly of gelators, micropatterned poly(acrylic acid) (PAA) brushes are employed to create a local and controllable acidic environment. The results show that the gel formation can be well confined in the catalytic surface plane with dimensions ranging from micro‐ to centimeter. Furthermore, the gels show a preferential growth along the normal direction of the catalytic surface, and the thickness of the resultant gel patterns can be easily controlled by tuning the grafting density of PAA brushes. This work shows an effective “bottom‐up” strategy toward control over the spatial organization of materials and is expected to find promising applications in, e.g., microelectronics, tissue engineering, and biomedicine.     

Therapeutic‐Gas‐Responsive Hydrogel

Nitric oxide (NO) is a crucial signaling molecule with various functions in physiological systems. Due to its potent biological effect, the preparation of responsive biomaterials upon NO having temporally transient properties is a challenging task. This study represents the first therapeutic‐gas (i.e., NO)‐responsive hydrogel by incorporating a NO‐cleavable crosslinker. The hydrogel is rapidly swollen in response to NO, and not to other gases. Furthermore, the NO‐responsive gel is converted to enzyme‐responsive gels by cascade reactions from an enzyme to NO production for which the NO precursor is a substrate of the enzyme. The application of the hydrogel as a NO‐responsive drug‐delivery system is proved here by revealing effective protein drug release by NO infusion, and the hydrogel is also shown to be swollen by the NO secreted from the cultured cells. The NO‐responsive hydrogel may prove useful in many applications, for example drug‐delivery vehicles, inflammation modulators, and as a tissue scaffold.     

Layer‐By‐Layer Electropeeling of Organic Conducting Material Imaged In Real Time

Soft materials comprising low‐molecular‐weight organic molecules are attracting increasing interest because of their importance in the development of a number of emerging areas in nanoscience and technology, including molecular electronics, nanosystems for energy conversion, and devices in the widest sense. Their interaction with electrodes and their behavior under electric fields is a topic of vital significance for these areas, and about which very little is known. Here unprecedented evidence is presented for the controlled peeling of organic molecular material when a voltage is applied between the conducting system and the conducting probe of a scanning force microscope. The rate of removal of the material from the surface of the bulk conducting supramolecular material can be tuned. It depends on the potential applied and is initiated only above a threshold value of 200 mV. The results indicate the importance of electric fields on the stability and performance of conducting organic systems at the nanoscale.     

A Mechanoresponsive Phase‐Changing Electrolyte Enables Fabrication of High‐Output Solid‐State Photobioelectrochemical Devices from Pigment‐Protein Multilayers

Exploitation of natural photovoltaic reaction center pigment proteins in biohybrid architectures for solar energy harvesting is attractive due to their global abundance, environmental compatibility, and near‐unity quantum efficiencies. However, it is challenging to achieve high photocurrents in a device setup due to limitations imposed by low light absorbance by protein monolayers and/or slow long‐range diffusion of liquid‐phase charge carriers. In an attempt to enhance the photocurrent density achievable by pigment proteins, here, an alternative solid‐state device architecture enabled by a mechanoresponsive gel electrolyte that can be applied under nondenaturing conditions is demonstrated. The phase‐changing electrolyte gel provides a pervading biocompatible interface for charge conduction through highly absorbing protein multilayers that are fabricated in a simple fashion. Assembled devices exhibit enhanced current stability and a maximal photoresponse of ≈860 µA cm⁻², a fivefold improvement over the best previous comparable devices under standard illumination conditions. Photocurrent generation is enhanced by directional energy transfer through extended layers of light‐harvesting complexes, mimicking the modular antenna/transducer architecture of natural photosystems, and by metastable radical pair formation when photovoltaic reaction centers are embedded throughout light‐harvesting regions of the device.     

Self‐Assembled α‐Cyanostilbenes for Advanced Functional Materials

In the specific context of condensed media, the significant and increasing recent interest in the α‐cyanostilbene (CS) motif [? Ar? CH?C(CN)? Ar? ] is relevant. These compounds have shown remarkable optical features in addition to interesting electrical properties, and hence they are recognized as very suitable and versatile options for the development of functional materials. This progress report is focused on current and future use of CS structures and molecular assemblies with the aim of exploring and developing for the next generations of functional materials. A critical selection of illustrative materials that contain the CS motif, including relevant subfamilies such as the dicyanodistyrylbenzene and 2,3,3‐triphenylacrylonitrile shows how, driven by the self‐assembly of CS blocks, a variety of properties, effects, and possibilities for practical applications can be offered to the scientific community, through different rational routes for the elaboration of advanced materials. A survey is provided on the research efforts directed toward promoting the self‐assembly of the solid state (polycrystalline solids, thin films, and single crystals), liquid crystals, nanostructures, and gels with multistimuli responsiveness, and applications for sensors, organic light‐emitting diodes, organic field effect transistors, organic lasers, solar cells, or bioimaging purposes.