Topological Adhesion of Wet Materials

Achieving strong adhesion between wet materials (i.e., tissues and hydrogels) is challenging. Existing adhesives are weak, toxic, incompatible with wet and soft surfaces, or restricted to specific functional groups from the wet materials. The approach reported here uses biocompatible polymer chains to achieve strong adhesion and retain softness, but requires no functional groups from the wet materials. In response to a trigger, the polymer chains form a network, in topological entanglement with the two polymer networks of the wet materials, stitching them together like a suture at the molecular scale. To illustrate topological adhesion, pH is used as a trigger. The stitching polymers are soluble in water in one pH range but form a polymer network in another pH range. Several stitching polymers are selected to create strong adhesion between hydrogels in full range of pH, as well as between hydrogels and various porcine tissues (liver, heart, artery, skin, and stomach). The adhesion energy above 1000 J m^?2 is achieved when the stitching polymer network elicits the hysteresis in the wet materials. The molecular suture can be designed to be permanent, transient, or removable on‐demand. The topological adhesion may open many opportunities in complex and diverse environments.     

Tunable Photocontrolled Motions Using Stored Strain Energy in Malleable Azobenzene Liquid Crystalline Polymer Actuators

A new strategy for enhancing the photoinduced mechanical force is demonstrated using a reprocessable azobenzene‐containing liquid crystalline network (LCN). The basic idea is to store mechanical strain energy in the polymer beforehand so that UV light can then be used to generate a mechanical force not only from the direct light to mechanical energy conversion upon the trans–cis photoisomerization of azobenzene mesogens but also from the light‐triggered release of the prestored strain energy. It is shown that the two mechanisms can add up to result in unprecedented photoindued mechanical force. Together with the malleability of the polymer stemming from the use of dynamic covalent bonds for chain crosslinking, large‐size polymer photoactuators in the form of wheels or spring‐like “motors” can be constructed, and, by adjusting the amount of prestored strain energy in the polymer, a variety of robust, light‐driven motions with tunable rolling or moving direction and speed can be achieved. The approach of prestoring a controllable amount of strain energy to obtain a strong and tunable photoinduced mechanical force in azobenzene LCN can be further explored for applications of light‐driven polymer actuators.     

Dynamic Coordination of Eu–Iminodiacetate to Control Fluorochromic Response of Polymer Hydrogels to Multistimuli

New fluorochromic materials that reversibly change their emission properties in response to their environment are of interest for the development of sensors and light‐emitting materials. A new design of Eu‐containing polymer hydrogels showing fast self‐healing and tunable fluorochromic properties in response to five different stimuli, including pH, temperature, metal ions, sonication, and force, is reported. The polymer hydrogels are fabricated using Eu–iminodiacetate (IDA) coordination in a hydrophilic poly(N,N‐dimethylacrylamide) matrix. Dynamic metal–ligand coordination allows reversible formation and disruption of hydrogel networks under various stimuli which makes hydrogels self‐healable and injectable. Such hydrogels show interesting switchable ON/OFF luminescence along with the sol–gel transition through the reversible formation and dissociation of Eu–IDA complexes upon various stimuli. It is demonstrated that Eu‐containing hydrogels display fast and reversible mechanochromic response as well in hydrogels having interpenetrating polymer network. Those multistimuli responsive fluorochromic hydrogels illustrate a new pathway to make smart optical materials, particularly for biological sensors where multistimuli response is required.     

Liquid‐Crystalline Dynamic Networks Doped with Gold Nanorods Showing Enhanced Photocontrol of Actuation

A near‐infrared‐light (NIR)‐ and UV‐light‐responsive polymer nanocomposite is synthesized by doping polymer‐grafted gold nanorods into azobenzene liquid‐crystalline dynamic networks (AuNR‐ALCNs). The effects of the two different photoresponsive mechanisms, i.e., the photochemical reaction of azobenzene and the photothermal effect from the surface plasmon resonance of the AuNRs, are investigated by monitoring both the NIR‐ and UV‐light‐induced contraction forces of the oriented AuNR‐ALCNs. By taking advantage of the material's easy processability, bilayer‐structured actuators can be fabricated to display photocontrollable bending/unbending directions, as well as localized actuations through programmed alignment of azobenzene mesogens in selected regions. Versatile and complex motions enabled by the enhanced photocontrol of actuation are demonstrated, including plastic “athletes” that can execute light‐controlled push‐ups or sit‐ups, and a light‐driven caterpillar‐inspired walker that can crawl forward on a ratcheted substrate at a speed of about 13 mm min^‐1. Moreover, the photomechanical effects arising from the two types of light‐triggered molecular motion, i.e., the trans–cis photoisomerization and a liquid‐crystalline–isotropic phase transition of the azobenzene mesogens, are added up to design a polymer “crane” that is capable of performing light‐controlled, robot‐like, concerted macroscopic motions including grasping, lifting up, lowering down, and releasing an object.     

Hydrogel Paint

For a hydrogel coating on a substrate to be stable, covalent bonds polymerize monomer units into polymer chains, crosslink the polymer chains into a polymer network, and interlink the polymer network to the substrate. The three processes—polymerization, crosslinking, and interlinking—usually concur. This concurrency hinders widespread applications of hydrogel coatings. Here a principle is described to create hydrogel paints that decouple polymerization from crosslinking and interlinking. Like a common paint, a hydrogel paint divides the labor between the paint maker and the paint user. The paint maker formulates the hydrogel paint by copolymerizing monomer units and coupling agents into polymer chains, but does not crosslink them. The paint user applies the paint on various materials (elastomer, plastic, glass, ceramic, or metal), and by various operations (brush, cast, dip, spin, or spray). During cure, the coupling agents crosslink the polymer chains into a network and interlink the polymer network to the substrate. As an example, hydrogels with thickness in the range of 2–20 µm are dip coated on medical nitinol wires. The coated wires reduce friction by eightfold, and remain stable over 50 test cycles. Also demonstrated are several proof‐of‐concept applications, including stimuli‐responsive structures and antifouling model boats.     

Proteolytically Degradable Photo‐Polymerized Hydrogels Made From PEG–Fibrinogen Adducts

We develop a biomaterial based on protein–polymer conjugates where poly(ethylene glycol) (PEG) polymer chains are covalently linked to multiple thiols on denatured fibrinogen. We hypothesize that conjugation of large diacrylate‐functionalized linear PEG chains to fibrinogen could govern the molecular architecture of the polymer network via a unique protein–polymer interaction. The hypothesis is explored using carefully designed shear rheometry and swelling experiments of the hydrogels and their precursor PEG/fibrinogen conjugate solutions. The physical properties of non‐cross‐linked and UV cross‐linked PEGylated fibrinogen having PEG molecular weights ranging from 10 to 20 kDa are specifically investigated. Attaching multiple hydrophilic, functionalized PEG chains to the denatured fibrinogen solubilizes the denatured protein and enables a rapid free‐radical polymerization cross‐linking reaction in the hydrogel precursor solution. As expected, the conjugated protein‐polymer macromolecular complexes act to mediate the interactions between radicals and unsaturated bonds during the free‐radical polymerization reaction, when compared to control PEG hydrogels. Accordingly, the cross‐linking kinetics and stiffness of the cross‐linked hydrogel are highly influenced by the protein–polymer conjugate architecture and molecular entanglements arising from hydrophobic/hydrophilic interactions and steric hindrances. The proteolytic degradation products of the protein–polymer conjugates proves to be were different from those of the non‐conjugated denatured protein degradation products, indicating that steric hindrances may alter the proteolytic susceptibility of the PEG–protein adduct. A more complete understanding of the molecular complexities associated with this type of protein‐polymer conjugation can help to identify the full potential of a biomaterial that combines the advantages of synthetic polymers and bioactive proteins.     

A Solvent-Exchange Strategy to Regulate Noncovalent Interactions for Strong and Antiswelling Hydrogels

Physical hydrogels from existing polymers consisting of noncovalent interacting networks are highly desired due to their well-controlled compositions and environmental friendliness; and therefore, applied as adhesives, artificial tissues, and soft machines. Nevertheless, these gels have suffered from weak mechanical strength and low water resistance. Current methodologies used to fabricate these hydrogels mainly involve the freezing–thawing process (cryogels), which are complicated in preparation and short in adjustment of polymer conformation. Here, taking the merits of noncovalent bonds in adjustability and reversibility, a solvent-exchange strategy is developed to construct a class of exogels. Based on the exchange from a good solvent subsequently to a poor one, the intra- and interpolymer interactions are initially suppressed and then recovered, resulting in dissolving and cross-linking to polymers, respectively. Key to this approach is the good solvent, which favors of a stretched polymer conformation to homogenize the network, forming cross-linked hydrogel networks with remarkable stiffness, toughness, antiswelling properties, and thus underwater adhesive performance. The exogels highlight a facile but highly effective strategy of turning the solvent and consequently the noncovalent interactions to achieve the rational design of enhanced hydrogels and hydrogel-based soft materials.     

Switchable Adhesion of Micropillar Adhesive on Rough Surfaces

Switchable structured adhesion on rough surfaces is highly desired for a wide range of applications. Combing the advantages of gecko seta and creeper root, a switchable fibrillar adhesive composed of polyurethane (PU) as the backing layer and graphene/shape memory polymer (GSMP) as the pillar array is developed. The photothermal effect of graphene (under UV irradiation) changes GSMP micropillars into the viscoelastic state, allowing easy and intimate contact on surfaces with a wide range of roughness. By controlling the phase state of GSMP via UV irradiation during detachment, the GSMP micropillar array can be switched between the robust‐adhesion state (UV off) and low‐adhesion state (UV on). The state of GSMP micropillars determines the adhesion force capacity and the stress distribution at the detaching interface, and therefore the adhesion performance. The PU‐GSMP adhesive achieves large adhesion strength (278 kPa), high switching ratio (29), and fast switching (10 s) at the same time. The results suggest a design principle for bioinspired structured adhesives, especially for reversible adhesion on surfaces with a wide range of roughness.     

Stabilization of Polymer‐Hydrogel Capsules via Thiol–Disulfide Exchange

Polymer hydrogels are used in diverse biomedical applications including drug delivery and tissue engineering. Among different chemical linkages, the natural and reversible thiol–disulfide interconversion is extensively explored to stabilize hydrogels. The creation of macro‐, micro‐, and nanoscale disulfide‐stabilized hydrogels commonly relies on the use of oxidizing agents that may have a detrimental effect on encapsulated cargo. Herein an oxidization‐free approach to create disulfide‐stabilized polymer hydrogels via a thiol–disulfide exchange reaction is reported. In particular, thiolated poly(methacrylic acid) is used and the conditions of polymer crosslinking in solution and on colloidal porous and solid microparticles are established. In the latter case, removal of the core particles yields stable, hollow, disulfide‐crosslinked hydrogel capsules. Further, a procedure is developed to achieve efficient disulfide crosslinking of multilayered polymer films to obtain stable, liposome‐loaded polymer‐hydrogel capsules that contain functional enzymatic cargo within the liposomal subcompartments. This approach is envisaged to facilitate the development of biomedical applications of hydrogels, specifically those including fragile cargo.     

Molding Micropatterns of Elasticity on PEG‐Based Hydrogels to Control Cell Adhesion and Migration

We present an innovative and simple, soft UV lithographic method “FIll‐Molding In Capillaries” (FIMIC) that combines soft lithography with capillary force driven filling of micro‐channels to create smooth hydrogel substrates with a 2D micro‐pattern on the surface. The lithographic procedure involves the molding of a polymer; in our case a bulk PEG‐based hydrogel, via UV‐curing from a microfabricated silicon master. The grooves of the created regular line pattern are consequently filled with a second hydrogel by capillary action. As a result, a smooth surface is obtained with a well‐defined pattern design of the two different polymers on its surface. The FIMIC method is very versatile; the only prerequisite is that the second material is liquid before curing in order to enable the filling process. In this specific case we present the proof of principle of this method by applying two hydrogels which differ in their crosslinking density and therefore in their elasticity. Preliminary cell culture studies on the fabricated elasticity patterned hydrogels indicate the preferred adhesion of the cells to the stiffer regions of the substrates, which implies that the novel substrates are a very useful platform for systematic cell migration studies, e.g. more fundamental investigation of the concept of “durotaxis”.     

Highly Tough Bioinspired Ternary Hydrogels Synergistically Reinforced by Graphene/Xonotlite Network

The application fields of hydrogels are often severely limited by their weak mechanical performance. It is therefore highly demanded to develop an effective strategy to fabricate mechanically strong hydrogels. Herein, a kind of bioinspired ternary hydrogel consisting of graphene oxide (GO) nanosheets, xonotlite nanowires, and polyacrylamide (PAM) is constructed under the synergy of hydrogen bonding–induced GO/xonotlite network and the penetrated PAM chain network. Benefiting from the effective energy dissipation mechanism caused by double–network structural design and the strong hydrogen bonding interaction between two nanobuilding blocks, the gel exhibits a high toughness of 22 MJ m⁻³ at an elongation of 2750%. Even notched with 1/4 size, it still holds a large extensibility of 2180% its initial length. These high‐performance hydrogels could be of great interest in the fields of tissue engineering and biomedical areas.     

A Novel Design of Multi‐Mechanoresponsive and Mechanically Strong Hydrogels

A newly developed polyacrylamide‐co ‐methyl acrylate/spiropyran (SP) hydrogel crosslinked by SP mechanophore demonstrates multi‐stimuli‐responsive and mechanically strong properties. The hydrogels not only exhibit thermo‐, photo‐, and mechano‐induced color changes, but also achieve super‐strong mechanical properties (tensile stress of 1.45 MPa, tensile strain of ≈600%, and fracture energy of 7300 J m^?2). Due to a reversible structural transformation between spiropyran (a ring‐close) and merocyanine (a ring‐open) states, simple exposure of the hydrogels to white light can reverse color changes and restore mechanical properties. The new design approach for a new mechanoresponsive hydrogel is easily transformative to the development of other mechanophore‐based hydrogels for sensing, imaging, and display applications.     

Muscle‐Inspired Highly Anisotropic,Strong, Ion‐Conductive Hydrogels

Biological tissues generally exhibit excellent anisotropic mechanical properties owing to their well‐developed microstructures. Inspired by the aligned structure in muscles, a highly anisotropic, strong, and conductive wood hydrogel is developed by fully utilizing the high–tensile strength of natural wood, and the flexibility and high‐water content of hydrogels. The wood hydrogel exhibits a high–tensile strength of 36 MPa along the longitudinal direction due to the strong bonding and cross‐linking between the aligned cellulose nanofibers (CNFs) in wood and the polyacrylamide (PAM) polymer. The wood hydrogel is 5 times and 500 times stronger than the bacterial cellulose hydrogels (7.2 MPa) and the unmodified PAM hydrogel (0.072 MPa), respectively, representing one of the strongest hydrogels ever reported. Due to the negatively charged aligned CNF, the wood hydrogel is also an excellent nanofluidic conduit with an ionic conductivity of up to 5 × 10^?4 S cm^–1 at low concentrations for highly selective ion transport, akin to biological muscle tissue. The work offers a promising strategy to fabricate a wide variety of strong, anisotropic, flexible, and ionically conductive wood‐based hydrogels for potential biomaterials and nanofluidic applications.     

Multifunctional Superamphiphobic TiO2 Nanostructure Surfaces with Facile Wettability and Adhesion Engineering

Compared to conventional top‐down photo‐cleavage method, a facile bottom‐up ink‐combination method to in situ and rapidly achieve water wettability and adhesion transition, with a great contrast on the superamphiphobic TiO₂ nanostructured film, is described. Moreover, such combination method is suitable for various kinds of superamphiphobic substrate. Oil‐based ink covering or removing changes not only the topographical morphology but also surface chemical composition, and these resultant topographical morphology and composition engineering realize the site‐selectively switchable wettability varying from superamphiphobicity to amphiphilicity, and water adhesion between sliding superamphiphobicity and sticky superamphiphobicity in micro‐scale. Additionally, positive and negative micro‐pattern can be achieved by taking advantage of the inherent photocatalytic property of TiO₂ with the assistance of anti‐UV light ink mask. Finally, the potential applications of the site‐selectively sticky superamphiphobic surface were demonstrated. In a proof‐of‐concept study, the microdroplet manipulation (storage, moving, mixing, and transfer), specific gas sensing, wettability template for positive and negative ZnO patterning, and site‐selective cell immobilization have been demonstrated. This study will give an important input to the field of advanced functional material surfaces with special wettability.     

Tough Hydrogels with Fast,Strong, and Reversible Underwater Adhesion Based on a Multiscale Design

Hydrogels have promising applications in diverse areas, especially wet environments including tissue engineering, wound dressing, biomedical devices, and underwater soft robotics. Despite strong demands in such applications and great progress in irreversible bonding of robust hydrogels to diverse synthetic and biological surfaces, tough hydrogels with fast, strong, and reversible underwater adhesion are still not available. Herein, a strategy to develop hydrogels demonstrating such characteristics by combining macroscale surface engineering and nanoscale dynamic bonds is proposed. Based on this strategy, excellent underwater adhesion performance of tough hydrogels with dynamic ionic and hydrogen bonds, on diverse substrates, including hard glasses, soft hydrogels, and biological tissues is obtained. The proposed strategy can be generalized to develop other soft materials with underwater adhesion.     

D型Fmoc-苯丙氨酸/透明质酸复合双网络水凝胶的制备及应用

将N-芴甲氧羰基-D-苯丙氨酸(Fmoc-DPhe)和甲基丙烯酸缩水甘油酯(Glycidyl methacrylate,GMA)修饰的透明质酸(HA-GMA)在磷酸缓冲液中共混加热,冷却后Fmoc-DPhe分子先自组装形成超分子水凝胶,超分子水凝胶中的HA-GMA再经光照引发交联制备双网络复合水凝胶。研究该双网络水凝胶的力学性能、光学性质、微观形貌、药物缓释能力和抑菌性能。研究结果表明,双网络水凝胶比HA-GMA单网络水凝胶的力学性能强一倍左右且HA-GMA网络存在于双网络水凝胶中;光学性质显示双网络水凝胶中存在Fmoc-DPhe网络;微观形貌表明有两种水凝胶网络均存在于复合水凝胶中。当复合水凝胶包裹小分子模拟药物后,复合水凝胶达到模拟药物最大累积释放量的时间要比Fmoc-DPhe单网络水凝胶的长6 h;针对革兰氏阳性细菌的抑菌能力研究显示,双网络水凝胶的抑菌效果也比Fmoc-DPhe单网络水凝胶的更好。      

Cooling‐Triggered Shapeshifting Hydrogels with Multi‐Shape Memory Performance

Heating‐triggered shape actuation is vital for biomedical applications. The likely overheating and subsequent damage of surrounding tissue, however, severely limit its utilization in vivo. Herein, cooling‐triggered shapeshifting is achieved by designing dual‐network hydrogels that integrate a permanent network for elastic energy storage and a reversible network of hydrophobic crosslinks for “freezing” temporary shapes when heated. Upon cooling to 10 °C, the hydrophobic interactions weaken and allow recovery of the original shape, and thus programmable shape alterations. Further, multiple temporary shapes can be encoded independently at either different temperatures or different times during the isothermal network formation. The ability of these hydrogels to shapeshift at benign conditions may revolutionize biomedical implants and soft robotics.     

Design and Applications of Photoresponsive Hydrogels

Hydrogels are the most relevant biochemical scaffold due to their tunable properties, inherent biocompatibility, and similarity with tissue and cell environments. Over the past decade, hydrogels have developed from static materials to “smart” responsive materials adapting to various stimuli, such as pH, temperature, chemical, electrical, or light. Light stimulation is particularly interesting for many applications because of the capability of contact‐free remote manipulation of biomaterial properties and inherent spatial and temporal control. Moreover, light can be finely adjusted in its intrinsic properties, such as wavelength and intensity (i.e., the energy of an individual photon as well as the number of photons over time). Water is almost transparent for light in the photochemically relevant range (NIR–UV), thus hydrogels are well‐suited scaffolds for light‐responsive functionality. Hydrogels' chemical and physical variety combined with light responsiveness makes photoresponsive hydrogels ideal candidates for applications in several fields, ranging from biomaterials, medicine to soft robotics. Herein, the progress and new developments in the field of light‐responsive hydrogels are elaborated by first introducing the relevant photochemistries before discussing selected applications in detail.     

Remote Light‐Responsive Nanocarriers for Controlled Drug Delivery: Advances and Perspectives

Engineering of smart photoactivated nanomaterials for targeted drug delivery systems (DDS) has recently attracted considerable research interest as light enables precise and accurate controlled release of drug molecules in specific diseased cells and/or tissues in a highly spatial and temporal manner. In general, the development of appropriate light‐triggered DDS relies on processes of photolysis, photoisomerization, photo‐cross‐linking/un‐cross‐linking, and photoreduction, which are normally sensitive to ultraviolet (UV) or visible (Vis) light irradiation. Considering the issues of poor tissue penetration and high phototoxicity of these high‐energy photons of UV/Vis light, recently nanocarriers have been developed based on light‐response to low‐energy photon irradiation, in particular for the light wavelengths located in the near infrared (NIR) range. NIR light‐triggered drug release systems are normally achieved by using two‐photon absorption and photon upconversion processes. Herein, recent advances of light‐responsive nanoplatforms for controlled drug release are reviewed, covering the mechanism of light responsive small molecules and polymers, UV and Vis light responsive nanocarriers, and NIR light responsive nanocarriers. NIR‐light triggered drug delivery by two‐photon excitation and upconversion luminescence strategies is also included. In addition, the challenges and future perspectives for the development of light triggered DDS are highlighted.     

Highly Elastic and Ultratough Hybrid Ionic–Covalent Hydrogels with Tunable Structures and Mechanics

Hybrid ionically–covalently crosslinked double‐network (DN) hydrogels are attracting increasing attention on account of their self‐recovery ability and fatigue resistance, but their relative low mechanical strength and tedious performance adjustment severely limit their applications. Herein, a new strategy to concurrently fabricate hybrid ionic–covalent DN hydrogels and modulate their structures and mechanics is reported, in which an in situ formed chitosan ionic network is incorporated by post‐crosslinking the chitosan‐based composite hydrogel using multivalent anions solutions. The obtained hybrid DN hydrogels exhibit predominant mechanical properties including superior elastic modulus, high tensile strength, and ultrahigh fracture energy because of the more efficient energy dissipation of rigid short‐chain chitosan network. Notably, the swollen hydrogels still remain mechanically strong and tough even after immersion in water for 24 h. More significantly, simply changing the post‐crosslinking time can vary the compactness and rigidity of the chitosan network in situ, achieving flexible and efficient modulation of the structures and mechanics of the hybrid DN hydrogels. This study opens up a new horizon in the preparation and regulation of DN hydrogels for promising applications in tissue scaffolds, actuators, and wearable devices.