The pH-Sensitive Optical Fiber Integrated CMCS-PA@Fe Hydrogels for Photothermal Therapy and Real-Time Monitoring of Infected Wounds

Bacterial infections are one of the biggest threats to wound healing. Despite significant efforts in wound condition monitoring and treatment, significant challenges remain in real-time wound monitoring and timely treatment. Herein, a kind of hydrogel with dual functions, which can not only quickly diagnose wound bacterial infection but also provide timely and effective treatment is developed. First, Carborxymethy chitosan (CMCS)-Protocatechualdehyde (PA)@Fe hydrogels with double dynamic bonds are prepared by chelating PA@Fe with CMCS. Second, the pH-sensitive Polydimethylsiloxane (PDMS) optical fibers are integrated into the CMCS-PA@Fe hydrogels to obtain the pH-sensitive optical fiber/CMCS-PA@Fe hydrogels that exhibit good real-time monitoring of the wound healing process. The tissue adhesion and self-healing properties of the pH-sensitive optical fiber/CMCS-PA@Fe hydrogels can adapt to the movement and stretching of the skin. Meanwhile, with the assistance of the photothermal effect, the hydrogels have a high antibacterial effect (>99.9%). In addition, the pH-sensitive optical fiber/CMCS-PA@Fe hydrogels also show an excellent therapeutic effect in the wound infection model. Moreover, reliable and timely wound pH information can be sent to intelligent devices through microcomputers to monitor the healing status. Overall, the pH-sensitive optical fiber/CMCS-PA@Fe hydrogels provide an entirely new platform for developing smart, real-time diagnostics and timely wound treatment.     

Modular and Versatile Spatial Functionalization of Tissue Engineering Scaffolds through Fiber‐Initiated Controlled Radical Polymerization

Native tissues are typically heterogeneous and hierarchically organized, and generating scaffolds that can mimic these properties is critical for tissue engineering applications. By uniquely combining controlled radical polymerization (CRP), end‐functionalization of polymers, and advanced electrospinning techniques, a modular and versatile approach is introduced to generate scaffolds with spatially organized functionality. Poly‐ε‐caprolactone is end functionalized with either a polymerization‐initiating group or a cell‐binding peptide motif cyclic Arg‐Gly‐Asp‐Ser (cRGDS), and are each sequentially electrospun to produce zonally discrete bilayers within a continuous fiber scaffold. The polymerization‐initiating group is then used to graft an antifouling polymer bottlebrush based on poly(ethylene glycol) from the fiber surface using CRP exclusively within one bilayer of the scaffold. The ability to include additional multifunctionality during CRP is showcased by integrating a biotinylated monomer unit into the polymerization step allowing postmodification of the scaffold with streptavidin‐coupled moieties. These combined processing techniques result in an effective bilayered and dual‐functionality scaffold with a cell‐adhesive surface and an opposing antifouling non‐cell‐adhesive surface in zonally specific regions across the thickness of the scaffold, demonstrated through fluorescent labelling and cell adhesion studies. This modular and versatile approach combines strategies to produce scaffolds with tailorable properties for many applications in tissue engineering and regenerative medicine.     

Sequence‐Optimized Peptide Nanofibers as Growth Stimulators for Regeneration of Peripheral Neurons

There is an urgent need for biomaterials that support tissue healing, particularly neuronal regeneration. In a medium throughput screen novel self‐assembling peptide (SAP) sequences that form fibrils and stimulated nerve fiber growth of peripheral nervous system (PNS)‐derived neurons are identified. Based on the peptide sequences and fibril morphologies and by applying rational data‐mining, important structural parameters stimulating neuronal activity are elucidated. Three SAPs (SAP^1e, SAP^2e, and SAP^5c) enhance adhesion and growth of PNS neurons. These SAPs form 2D and 3D matrices that serve as bioactive scaffolds stimulating cell adhesion and growth. The newly discovered SAPs also support the growth of CNS neurons and glia cells. Subsequently, the potential of SAPs to enhance PNS regeneration in vivo is analyzed. For this, the facial nerve driving whisker movement in mice is injured. Notably, SAPs persist for up to 3 weeks in the injury site indicating highly adhesive properties and stability. After SAP administration, more motor neurons incorporating markers for successive regeneration are observed. Recovery of whisker movement is elevated in SAP‐injected mice. In summary, short peptides that form fibrils are identified and the adhesion, growth, and regeneration of neurons have been efficiently enhanced without the necessity to attach hormones or growth factors.     

Regulating Electrical Cue and Mechanotransduction in Topological Gradient Structure Modulated Piezoelectric Scaffolds to Predict Neural Cell Response

Neural cells respond to topographical cues with alterations in cell growth and neurite sprouting mediated by changes in cell behavior. The interaction of fiber topography with cell adhesion receptors affects how the cells adhere to the surface of fibers and defines cell fate through alterations in the biochemistry, physiology, and morphology of neural cells. Although previous studies suggest topographical features influence neural cell proliferation and neurite sprouting, only a few studies have attempted to assess the use of both electrical and topological cues in piezoelectric scaffolds for nerve regeneration. In this study, variations in the shape‐modified collectors enable tunable surface topographic constructs, from micropatterns to fiber bundle structure. The crystallinity, chemical composition, and quantitative analysis confirm that the interplay between the topological structures of the fibers and the blending of nanocomposite materials is critical for the formation of the β‐phase. It is found that the topographical features and induced electrical characteristics affect cell growth. Also, the intracellular signaling pathway is induced that can provide clues as to how neural cells respond to the topological gradient structure modulated piezoelectric scaffolds. An analysis of the neuron‐specific cytoskeletal related markers further reveals that the specific topographical features piezoelectric fibrous scaffold reinforces neuron‐specific cytoskeletal proteins and microtubule assembly.     

Mussel‐Inspired Contact‐Active Antibacterial Hydrogel with High Cell Affinity,Toughness, and Recoverability

Antibacterial hydrogel has received extensive attention in soft tissue repair, especially preventing infections those associated with impaired wound healing. However, it is challenging in developing an inherent antibacterial hydrogel integrating with excellent cell affinity and superior mechanical properties. Inspired by the mussel adhesion chemistry, a contact‐active antibacterial hydrogel is proposed by copolymerization of methacrylamide dopamine (MADA) and 2‐(dimethylamino)ethyl methacrylate and forming an interpenetrated network with quaternized chitosan. The reactive catechol groups of MADA endow the hydrogel with contact intensified bactericidal activity, because it increases the exposure of bacterial cells to the positively charged groups of the hydrogel and strengthens the bactericidal effect. MADA also maintains the good adhesion of fibroblasts to the hydrogel. Moreover, the hybrid chemical and physical cross‐links inner the hydrogel network makes the hydrogel strong and tough with good recoverability. In vitro and in vivo tests demonstrate that this tough and contact‐active antibacterial hydrogel is a promising material to fulfill the dual functions of promoting tissue regeneration and preventing bacterial infection for wound‐healing applications.     

Patterned Hydrogels for Controlled Platelet Adhesion from Whole Blood and Plasma

This work describes the preparation and properties of hydrogel surface chemistries enabling controlled and well‐defined cell adhesion. The hydrogels may be prepared directly on plastic substrates, such as polystyrene slides or dishes, using a quick and experimentally simple photopolymerization process, compatible with photolithographic and microfluidic patterning methods. The intended application for these materials is as substrates for diagnostic cell adhesion assays, particularly for the analysis of human platelet function. The non‐specific adsorption of fibrinogen, a platelet adhesion promoting protein, is shown to be completely inhibited by the hydrogel, provided that the film thickness is sufficient (>5 nm). This allows the hydrogel to be used as a matrix for presenting selected bioactive ligands without risking interference from non‐specifically adsorbed platelet adhesion factors, even in undiluted whole blood and blood plasma. This concept is demonstrated by preparing patterns of proteins on hydrogel surfaces, resulting in highly controlled platelet adhesion. Further insights into the protein immobilization and platelet adhesion processes are provided by studies using imaging surface plasmon resonance. The hydrogel surfaces used in this work appear to provide an ideal platform for cell adhesion studies of platelets, and potentially also for other cell types.     

Association between Cell Microenvironment Altered by Gold Nanowire Array and Regulation of Partial Epithelial-Mesenchymal Transition

Cell microenvironment is an essential factor in determining cell growth and cell fate. Many studies have been carried out to understand the functions and mechanisms of small molecules or growth factors/cytokines; however, the effects of the physical environment on cells are relatively unknown. Changes in the cell's physical microenvironment affect cell adhesion and modify intracellular signaling controlled by adhesion properties, resulting in altering the cytoskeletal structure and cellular properties. Herein, it is demonstrated that the changes in cell adhesion can affect the epithelial-mesenchymal transition (EMT) of epithelial cells by implementing a cell microenvironment with a gold (Au) nanowire array to influence cell adhesion. A forcible decrease in cell adhesion leads to the downregulation of epithelial biomarkers and the upregulation of mesenchymal biomarkers. The results of force-distance experiments using atomic force microscopy showed that the overall stiffness of epithelial cells declined similarly to the case for mesenchymal-like cells. With this comprehensive analysis of cellular properties, a physical microenvironment for cell adhesion alteration is suggested, that can induce mesenchymal characteristics in both epithelial and mesenchymal cells through partial EMT.     

Bioinspired Multifunctional Hybrid Hydrogel Promotes Wound Healing

Inspired by the coordinated multiple healing mechanism of the organism, a four‐armed benzaldehyde‐terminated polyethylene glycol and dodecyl‐modified chitosan hybrid hydrogel with vascular endothelial growth factor (VEGF) encapsulation are presented for efficient and versatile wound healing. The hybrid hydrogel is formed through the reversible Schiff base and possesses self‐healing capability. As the dodecyl tails can insert themselves into and be anchored onto the lipid bilayer of the cell membrane, the hybrid hydrogel has outstanding tissue adhesion, blood cell coagulation and hemostasis, anti‐infection, and cell recruitment functions. Moreover, by loading in and controllably releasing VEGF from the hybrid hydrogel, the processes of cell proliferation and tissue remodeling in the wound bed can be significantly improved. Based on an in vivo study of the multifunctional hybrid hydrogel, it is demonstrated that acute tissue injuries such as vessel bleeding and liver bleeding can be repaired immediately because of the outstanding adhesion and hemostasis features of the hydrogel. Moreover, the chronic wound‐healing process of an infectious full‐thickness skin defect model can also be significantly enhanced by promoting angiogenesis, collagen deposition, macrophage polarization, and granulation tissue formation. Thus, this multifunctional hybrid hydrogel is potentially valuable for clinical applications.     

Anti-Dehydration and Rapid Trigger-Detachable Multifunctional Hydrogels Promote Scarless Therapeutics of Deep Burn

There are issues and challenges in treating deep burns because of the long recovery time, frequent dressing changes, wound infection, and easy to form scar that influence aesthetics. Besides, some specific tissues are not suitable for large dressing coverage (e.g., face, perineum). Therefore, an ideal deep burn dressing should have good adhesion properties to fit the wound effectively, painless and quick replacement, resistant to infection, accelerate wound healing, reduce scarring and facilitate monitoring and diagnosis. Herein, an anti-dehydration and rapid-trigger multifunctional hydrogel dressing is prepared by interface reaction. The Pacrylamide-Formylboronicacid-Tannic acid (PAFT) hydrogels are prepared by a simple method on anti-dehydration elastomeric membrane, which is obtained using tannic acid as a dynamic cross-linking agent with 3-formylboronic acid and acrylamideunder UV light. The hydrogel exhibits a strong interfacial adhesion (892 J m⁻² ± 65 J m⁻²), which rapidly (2 min) decreases (to 180 J m⁻² ± 20 J m⁻²) when in the presence of glucose solution. The hydrogel has excellent anti-dehydration and moisturizing properties, and also exhibits superior antibacterial properties, hemostasis, and biocompatibility. This hydrogel is transparent allowing effective observation of wound transformation and therapeutics. Moreover, PAFT hydrogel accelerates the healing of deep burns and reduces scars.     

Autonomic Recovery of Fiber/Matrix Interfacial Bond Strength in a Model Composite

Autonomic self‐healing of interfacial damage in a model single‐fiber composite is achieved through sequestration of ca. 1.5 μm diameter dicyclopentadiene (DCPD) healing‐agent‐filled capsules and recrystallized Grubbs’ catalyst to the fiber/matrix interface. When damage initiates at the fiber/matrix interface, the capsules on the fiber surface rupture, and healing agent is released into the crack plane where it contacts the catalyst, initiating polymerization. A protocol for characterizing the efficiency of interfacial healing for the single‐fiber system is established. Interfacial shear strength (IFSS), a measure of the bond strength between the fiber and matrix, is evaluated for microbond specimens consisting of a single self‐healing functionalized fiber embedded in a microdroplet of epoxy. The initial (virgin) IFSS is equivalent or enhanced by the addition of capsules and catalyst to the interface and up to 44% average recovery of IFSS is achieved in self‐healing samples after full interfacial debonding. Examination of the fracture interfaces by scanning electron microscopy reveals further evidence of a polyDCPD film in self‐healing samples. Recovery of IFSS is dictated by the bond strength of polyDCPD to the surrounding epoxy matrix.     

Self‐healing Fibers: Autonomic Recovery of Fiber/Matrix Interfacial Bond Strength in a Model Composite (Adv. Funct. Mater. 20/2010)

Autonomic self‐healing of interfacial damage in a model single‐fiber composite is achieved through sequestration of ca. 1.5 μm diameter dicyclopentadiene (DCPD) healing‐agent‐filled capsules and recrystallized Grubbs’ catalyst to the fiber/matrix interface. When damage initiates at the fiber/matrix interface, the capsules on the fiber surface rupture, and healing agent is released into the crack plane where it contacts the catalyst, initiating polymerization. A protocol for characterizing the efficiency of interfacial healing for the single‐fiber system is established. Interfacial shear strength (IFSS), a measure of the bond strength between the fiber and matrix, is evaluated for microbond specimens consisting of a single self‐healing functionalized fiber embedded in a microdroplet of epoxy. The initial (virgin) IFSS is equivalent or enhanced by the addition of capsules and catalyst to the interface and up to 44% average recovery of IFSS is achieved in self‐healing samples after full interfacial debonding. Examination of the fracture interfaces by scanning electron microscopy reveals further evidence of a polyDCPD film in self‐healing samples. Recovery of IFSS is dictated by the bond strength of polyDCPD to the surrounding epoxy matrix.     

Piezoelectric Nanotopography Induced Neuron‐Like Differentiation of Stem Cells

The biophysical characteristics of the extracellular matrix, such as nanotopography and bioelectricity, have a profound influence on cell proliferation, adhesion, differentiation, etc. Recognition of the function of a certain biophysical cue and fabrication of biomaterial scaffolds with specific properties would have important implications and significant applications in tissue engineering. Herein, nanotopographic and piezoelectric biomaterials are fabricated and the combination effect of and individual contribution to proliferation, adhesion, and neuron‐like differentiation of rat bone marrow‐derived mesenchymal stem cells (rbMSCs) are clarified via nanotopography and piezoelectricity. Piezoelectric polyvinylidene fluoride with nanostripe array structures is fabricated, which can generate a surface piezoelectric potential up to millivolt by cell movement and traction. The results reveal a more favorable effect on neuron‐like differentiation of rbMSCs from the combination of piezoelectricity and nanotopography rather than nanotopography alone, whereas nanotopography can increase cellular adhesion. This research provides a new insight into designing biomaterials for the potential application in neural tissue engineering.     

Impact of Reactive Amphiphilic Copolymers on Mechanical Properties and Cell Responses of Fibrin‐Based Hydrogels

Mechanical properties of hydrogels can be modified by the variation of structure and concentration of reactive building blocks. One promising biological source for the synthesis of biocompatible hydrogels is fibrinogen. Fibrinogen is a glycoprotein in blood, which can be transformed enzymatically to fibrin playing an important role in wound healing and clot formation. In the present work, it is demonstrated that hybrid hydrogels with their improved mechanical properties, tunable internal structure, and enhanced resistance to degradation can be synthesized by a combination of fibrinogen and reactive amphiphilic copolymers. Water‐soluble amphiphilic copolymers with tunable molecular weight and controlled amounts of reactive epoxy side groups are used as reactive crosslinkers to reinforce fibrin hydrogels. In the present work, copolymers that can influence the mechanical properties of fibrin‐based hydrogels are used. The reactive copolymers increase the storage modulus of the hydrogels from 600 Pa to 30 kPa. The thickness of fibrin fibers is regulated by the copolymer concentration. It could be demonstrated that the fibrin‐based hydrogels are biocompatible and support cell proliferation. Their degradation rate is considerably slower than that of native fibrin gels. In conclusion, fibrin‐based hydrogels with tunable elasticity and fiber thickness useful to direct cell responses like proliferation and differentiation are produced.     

Length‐Scale Mediated Differential Adhesion of Mammalian Cells and Microbes

Surfaces of implantable biomedical devices are increasingly engineered to promote their interactions with tissue. However, surfaces that stimulate desirable mammalian cell adhesion, spreading, and proliferation also enable microbial colonization. The biomaterials‐associated infection that can result is now a critical clinical problem. We have identified an important mechanism to create a surface that can simultaneously promote healing while reducing the probability of infection. Surfaces are created with submicrometer‐sized, non‐adhesive microgels patterned on an otherwise cell‐adhesive surface. Quantitative force measurements between a staphylococcus and a patterned surface show that the adhesion strength decreases significantly at inter‐gel spacings comparable to bacterial dimensions. Time‐resolved flow‐chamber measurements show that the microbial deposition rate dramatically decreases at these same spacings. Importantly, the adhesion and spreading of osteoblast‐like cells is preserved despite the sub‐cellular non‐adhesive surface features. Since such length‐scale‐mediated differential interactions do not rely on antibiotics, this mechanism can be particularly significant in mitigating biomaterials‐associated infection by antibiotic‐resistant bacteria such as MRSA.     

Bio-Multifunctional Hydrogel Patches for Repairing Full-Thickness Abdominal Wall Defects

Developing bio-multifunctional patches with natural extracellular matrix-like structures, excellent high adhesion in the wet state, self-healing ability, antibacterial activity, and favorable cell responses for accelerating tissue healing is highly desirable in clinical applications. Herein, bio-multifunctional composite hydrogels are developed by coupling carboxymethyl chitosan and 4-arm poly (ethylene glycol) aldehyde for full-thickness abdominal wall defect repair. The prepared hydrogels exhibit excellent self-healing and mechanical properties, high adhesion in the wet state, and significant antibacterial ability. In vitro cellular experiments show that the hydrogels combined with recombinant bovine basic fibroblast growth factor remarkably promote cell proliferation and then accelerate full-thickness abdominal wall defect repair in a rat model. The histomorphological evaluation shows that compared to the commercial polypropylene mesh used clinically, the designed hydrogel patches facilitate an increase in the thickness and integrity of the abdominal wall tissue by upregulating the production of Ki67, enhancing the formation of collagen, inducing neovascularization, and inhibiting inflammation by reducing the expression of IL-6, TNF-α, and IL-1β. The results demonstrate that this novel bio-multifunctional hydrogel patch holds great potential for the treatment of full-thickness abdominal wall defects.     

Glycopeptide-Based Multifunctional Hydrogels Promote Diabetic Wound Healing through pH Regulation of Microenvironment

Excessive inflammation, bacterial infection, and blocked angiogenesis make diabetic wound healing challenging. Multifunctional wound dressings have several advantages in diabetic wound healing. In addition, the pH regulation of the microenvironment is shown to be a key factor that promotes skin regeneration through cellular immune regulation. However, few reports have focused on the development of functional dressings with the ability to regulate the pH microenvironment and promote diabetic wound healing. This study presents a novel approach for regulating the pH microenvironment of diabetic wound sites using a glycopeptide-based hydrogel consisting of modified hyaluronic acid and poly(6-aminocaproic acid). This hydrogel forms a network through Schiff base interactions and metal complexation, which suppresses inflammation and accelerates angiogenesis during wound healing. Hydrogels not only have adequate mechanical properties and self-healing ability but can also support tissue adhesion. They can also promote the secretion of inducible cAMP early repressor, which promotes the polarization of macrophages toward the M2 type. The in vivo results confirm that hydrogel promotes diabetic wound repair and skin regeneration by exerting rapid anti-inflammatory effects and promoting angiogenesis. Therefore, this hydrogel system represents an effective strategy for treating diabetic wounds.     

Mussel‐Inspired Approach to Constructing Robust Multilayered Alginate Films for Antibacterial Applications

The exceptional mechanical properties of the byssus—the fibrous holdfast of mussels that provides underwater adhesion—have potential applications in medicine and technology. The catechol–Fe³⁺–catechol interaction underlies the unique properties of mussel byssus and has emerged as a tool for developing functional hybrid materials such as pH‐responsive, self‐healing gels. Herein, the construction of functional alginate (Alg) film on a solid substrate inspired by mussel byssus is reported. The approach consists of spin‐coating‐assisted deposition of Alg catechols onto a solid substrate and their subsequent crosslinking via catechol–Fe³⁺–catechol interactions. This yields robust and multilayered Alg films that are resistant to protein adsorption and suppress bacterial adhesion. This method can be used to create antibacterial films for coating implanted medical devices.     

Microfluidic Spinning of Cell‐Responsive Grooved Microfibers

Engineering living tissues that simulate their natural counterparts is a dynamic area of research. Among the various models of biological tissues being developed, fiber‐shaped cellular architectures, which can be used as artificial blood vessels or muscle fibers, have drawn particular attention. However, the fabrication of continuous microfiber substrates for culturing cells is still limited to a restricted number of polymers (e.g., alginate) having easy processability but poor cell–material interaction properties. Moreover, the typical smooth surface of a synthetic fiber does not replicate the micro‐ and nanofeatures observed in vivo, which guide and regulate cell behavior. In this study, a method to fabricate photocrosslinkable cell‐responsive methacrylamide‐modified gelatin (GelMA) fibers with exquisite microstructured surfaces by using a microfluidic device is developed. These hydrogel fibers with microgrooved surfaces efficiently promote cell encapsulation and adhesion. GelMA fibers significantly promote the viability of cells encapsulated in/or grown on the fibers compared with similar grooved alginate fibers used as controls. Importantly, the grooves engraved on the GelMA fibers induce cell alignment. Furthermore, the GelMA fibers exhibit excellent processability and could be wound into various shapes. These microstructured GelMA fibers have great potential as templates for the creation of fiber‐shaped tissues or tissue microstructures.     

Mussel Inspired Dynamic Cross‐Linking of Self‐Healing Peptide Nanofiber Network

A general drawback of supramolecular peptide networks is their weak mechanical properties. In order to overcome a similar challenge, mussels have adapted to a pH‐dependent iron complexation strategy for adhesion and curing. This strategy also provides successful stiffening and self‐healing properties. The present study is inspired by the mussel curing strategy to establish iron cross‐link points in self‐assembled peptide networks. The impact of peptide‐iron complexation on the morphology and secondary structure of the supramolecular nanofibers is characterized by scanning electron microscopy, circular dichroism and Fourier transform infrared spectroscopy. Mechanical properties of the cross‐linked network are probed by small angle oscillatory rheology and nanoindentation by atomic force microscopy. It is shown that iron complexation has no influence on self‐assembly and β‐sheet‐driven elongation of the nanofibers. On the other hand, the organic‐inorganic hybrid network of iron cross‐linked nanofibers demonstrates strong mechanical properties comparable to that of covalently cross‐linked network. Strikingly, iron cross‐linking does not inhibit intrinsic reversibility of supramolecular peptide polymers into disassembled building blocks and the self‐healing ability upon high shear load. The strategy described here could be extended to improve mechanical properties of a wide range of supramolecular polymer networks.     

Adhesion and Surface Interactions of a Self‐Healing Polymer with Multiple Hydrogen‐Bonding Groups

The surface properties and self‐adhesion mechanism of self‐healing poly(butyl acrylate) (PBA) copolymers containing comonomers with 2‐ureido‐4[1H]‐pyrimidinone quadruple hydrogen bonding groups (UPy) are investigated using a surface forces apparatus (SFA) coupled with a top‐view optical microscope. The surface energies of PBA–UPy4.0 and PBA–UPy7.2 (with mole percentages of UPy 4.0% and 7.2%, respectively) are estimated to be 45–56 mJ m^?2 under dry condition by contact angle measurements using a three probe liquid method and also by contact and adhesion mechanics tests, as compared to the reported literature value of 31–34 mJ m^?2 for PBA, an increase that is attributed to the strong UPy–UPy H‐bonding interactions. The adhesion strengths of PBA–UPy polymers depend on the UPy content, contact time, temperature and humidity level. Fractured PBA–UPy films can fully recover their self‐adhesion strength to 40, 81, and 100% in 10 s, 3 h, and 50 h, respectively, under almost zero external load. The fracture patterns (i.e., viscous fingers and highly “self‐organized” parallel stripe patterns) have implications for fabricating patterned surfaces in materials science and nanotechnology. These results provide new insights into the fundamental understanding of adhesive mechanisms of multiple hydrogen‐bonding polymers and development of novel self‐healing and stimuli‐responsive materials.