Self‐Healing,Injectable Gelatin Hydrogels Cross‐Linked by Dynamic Schiff Base Linkages Support Cell Adhesion and Sustained Release of Antibacterial Drugs

A new class of dynamic hydrogels made through Schiff base bonds based on gelatin (type A and B) and polyethylene glycol dibenzaldehyde (diBA‐PEG, 2000 and 4000 g mol^?1) is developed. Hydrogels form in situ by mixing aqueous solutions of gelatin and diBA‐PEG at a carefully adjusted pH. Compression test shows that the samples based on gelatin A are able to withstand at least ten cyclic loading/unloading without crack formation and significant permanent deformation. Self‐healing behavior of the hydrogel is proved by rheological measurements and also visual method. This hydrogel is proven to be injectable and nontoxic. Performance of the hydrogel in loading and delivery of clindamycin hydrochloride, as an antibacterial model drug, is evaluated against Staphylococcus aureus via antibacterial activity test. In vitro release of clindamycin hydrochloride is studied through an innovative method and it becomes clear that the release of clindamycin hydrochloride from this hydrogel follows a zero‐order kinetics.     

An Injectable Self‐Healing Multifluorescent Hydrogel Formed by Engineered Coiled‐Coil Polypeptide and Quantum Dots

An injectable and self‐healing multifluorescent hydrogel system based on engineered coiled‐coil polypeptide and CdSe@ZnS quantum dots (QDs) is developed. The mechanical properties of the PC₁₀A‐QD hydrogel are able to be tuned by changing the concentrations of PC₁₀A and QDs. The G′ of PC₁₀A hydrogel increases from 800 to 1000 Pa by doping 6 nm oil‐soluble CdSe@ZnS QDs. The PC₁₀A‐QD hydrogel can easily pass through a 26‐gauge needle without clogging. In addition, through interfacial assembly of PC₁₀A polypeptide on the surface of the PC₁₀A‐QD hydrogel, each of these hydrogel can self‐assemble into a multifluorescent hydrogel. This approach for preparation of injectable self‐healing multifluorescent hydrogels is expected to apply in biomedicine.     

Tannin‐Tethered Gelatin Hydrogels with Considerable Self‐Healing and Adhesive Performances

Hydrogels, especially the ones with self‐recovery and adhesive performances, have attracted more and more attention owing to their wide practical potential in the biomedical field involving cell delivery, wound filling, and tissue engineering. Tannic acid (TA), a nature‐derived gallol‐rich polyphenol, exhibits not only unique chelating properties with transition metal cations but also desirable anti‐oxidation properties and strong bonding capability to proteins and gelatin. Thus, taking advantage of the versatility of TA, a one‐pot method is proposed herein to produce TA‐modified gelatin hydrogels with the aid of NaIO₄ under basic conditions. By changing the amount of NaIO₄ used, the obtained hydrogels are covalently cross‐linked to different degrees and consequently exhibit diversity in their self‐healing and adhesive properties. The gelling time, viscoelasticity, and morphology of hydrogels are investigated, and when the feed molar ratio of NaIO₄ to TA is adjusted to 15:1, the fabricated hydrogel shows optimum self‐healing efficiency of 73% and adhesive strength of 36 kPa. Additionally, considering the completely natural origin of TA and gelatin, this study offers an original way for the fabrication of biocompatible self‐healing and adhesive materials.     

Self‐Healing Polysaccharide Hydrogel Based on Dynamic Covalent Enamine Bonds

A self‐healing polysaccharide hydrogel based on dynamic covalent enamine bonds has been prepared with a facile, cost‐effective, and eco‐friendly way. The polysaccharide hydrogel is obtained by mixing cellulose acetoacetate (CAA) aqueous solution with chitosan aqueous solution under room temperature. CAA is synthesized by reaction of cellulose with tert‐butyl acetoacetate (t‐BAA) in ionic liquid 1‐allyl‐3‐methylimidazolium chloride (AMIMCl). The structure and properties of CAA are characterized by FT‐IR, NMR, and solubility measurements. The results demonstrate that CAA possesses water solubility with a degree of substitution (DS) about 0.58–1.11. The hydrogel shows an excellent self‐healing behavior without other external stimuli and good stability under physiological conditions. Furthermore, the polysaccharide hydrogel exhibits pH responsive properties.

     

Superfast Self‐Healing and Photothermal Active Hydrogel with Nondefective Graphene as Effective Additive

2D graphene with high quality holds great promise in improving the performance of the hydrogels owing to its exceptional electronic, thermal, and mechanical properties. However, the structure defects existed in graphene restrict its further applications. Herein, a simple and green method of fabricating defect‐free graphene nanosheets with the assistance of supercritical carbon dioxide (SC CO₂) is designed. The graphene nanosheets directly assemble with acrylic acid monomer and clay, and a flexible semitransparent hydrogel is fabricated. Benefiting from the excellent properties of the defect‐free graphene, the hydrogel exhibits the high mechanical performance, superfast self‐healing capability, excellent conductivity, and super photothermal conversion efficiency. According to the advantages above, the graphene/poly(acrylic acid)/clay hydrogels can be used for intelligent sensors for disease diagnosis, artificial electronic skin, and military stealth materials in the near future.     

Flexible Polysaccharide Hydrogel with pH‐Regulated Recovery of Self‐Healing and Mechanical Properties

A self‐healable hydrogel with recoverable self‐healing and mechanical properties is reported. The hydrogel (coded as ACSH) crosslinked by Schiff base linkage contains two polysaccharides of acrylamide‐modified chitosan (AMCS) and oxidized alginate (ADA). Self‐healing and mechanical properties are heavily influenced by the crosslinking time. The hydrogel crosslinked for 2 h possesses better mechanical and self‐healing properties than hydrogel crosslinked for 24 h. Macroscopic test shows that hydrogel without self‐healing ability can recover the self‐repair and mechanical properties by adjusting the pHs. The recovery of self‐healing and mechanical properties relies on the pH sensitivity of the Schiff base linkage. Adjusting the pH to acid, the Schiff base linkage becomes unstable and breaks. Regulating the pH to neutral, reconstruction of Schiff base linkage leads to recovery of the self‐repair and mechanical properties. The recoverable self‐healing property can be cycled once breakage and reconstruction of the Schiff base linkage can be conducted. In addition, this study demonstrates that the hydrogel can be remodeled into different shapes based on self‐healing property of the hydrogel. It is anticipated that this self‐healable hydrogel with recoverable self‐healing and mechanical properties may open a new way to investigate self‐healing hydrogel and find potential applications in different biomedical fields.     

A Facile Strategy for Preparing Tough,Self‐Healing Double‐Network Hyaluronic Acid Hydrogels Inspired by Mussel Cuticles

Compared with hydrogel‐like biological tissues such as cartilage, muscles, and blood vessels, current hyaluronic acid hydrogels often suffer from poor toughness and limited self‐healing properties. Herein, a facile and generalizable strategy inspired by mussel cuticles is presented to fabricate tough and self‐healing double‐network hyaluronic acid hydrogels. These hydrogels are composed of ductile, reversible Fe³⁺‐catechol interaction primary networks, and secondarily formed brittle, irreversible covalent networks. Based on this design strategy, the hyaluronic acid hydrogels are demonstrated to exhibit reinforced mechanical strength while maintaining a rapid self‐healing property. In addition, by simply regulating pH or UV irradiation time, the mechanical properties of the hydrogels can be regulated conveniently through variations between the primary and secondary networks.     

Self‐Healing and Shape‐Memory Superconducting Devices

Intelligent materials possess the function of self‐judgment and self‐optimization while sensing external stimuli such as stress, temperature, moisture, pH, electric or magnetic fields, or light. Besides, they often require self‐healing—the ability to repair damage spontaneously—or shape‐memory—the ability to return from a deformed state to their original shape induced by an external stimulus. Introducing such intelligence into superconducting (SC) devices is highly desirable to meet the critical requirement of maintenance‐free performance. Here, self‐healing and shape‐memory functions are realized in liquid metal based SC devices using smart packaging polymers. Without deteriorating their superconductivity, the SC devices can repair themselves by simply raising the temperature, without any other treatment. Beyond the specific functions achieved here, this work sheds new light on future SC devices with advanced functions such as self‐diagnosis, self‐adjusting, and sensing.     

Self‐Detecting and Self‐Healing Reinforce Elastomer Doped with Aggregation‐Induced Emission Molecules

Most of elastomers for fabrication of comfortable epidermal devices and smart actuators produce responsive signals by the stimuli‐induced deformation. Herein, a dynamic visualization of external stimuli rather than the deformation through synthesis of a self‐healing poly(dimethylsiloxane) (PDMS)‐based elastomer doped with aggregation‐induced emission (AIE) molecules is reported. The self‐healing PDMS‐based elastomer is designed and synthesized through molecule integration of reversible multi‐strength H‐bonds and permanent covalent crosslink sites. The adjustment of the weight ratio of elastic cross‐linker offers tunable mechanical properties of the resultant elastomer. After doping such an elastomer with AIE molecules of 1,1,2,2‐tetrakis(4‐nitrophenyl)ethane, the elastomer composite displays strong on–off fluorescence depending upon mechanical damage and temperatures, which can be used to detect the breaking and self‐healing performances, as well as the temperature change. The strategy described here provides another way to develop smart polymeric elastomers for practical applications.     

Existing and Novel Biomaterials for Bone Tissue Engineering

The treatment of bone defects remains one of the major challenges in modern clinical practice. Nowadays, with the increased incidence of bone disease in an aging population, the demand for materials to repair bone defects continues to grow. Recent advances in the development of biomaterials offer new possibilities for exploring modern bone tissue engineering strategies. Both natural and synthetic biomaterials have been used for tissue repair. A variety of porous structures that promote cell adhesion, differentiation, and proliferation enable better implant integration with increasingly better physical properties. The selection of a suitable biomaterial on which the patient’s new tissue will grow is one of the key issues when designing a modern tissue scaffold and planning the entire treatment process. The purpose of this article is to present a comprehensive literature review of existing and novel biomaterials used in the surgical treatment of bone tissue defects. The materials described are divided into three groups—organic, inorganic, and synthetic polymers—taking into account current trends. This review highlights different types of existing and novel natural and synthetic materials used in bone tissue engineering and their advantages and disadvantages for bone defects regeneration.     

Multiple Shape Memory,Self‐Healable,and Supertough PAA‐GO‐Fe3+ Hydrogel

A multiple shape memory and self‐healing poly(acrylic acid)‐graphene oxide‐Fe³⁺ (PAA‐GO‐Fe³⁺) hydrogel with supertough strength is synthesized containing dual physically cross‐linked PAA network by GO and Fe³⁺. The first GO cross‐linked hydrogel can be reversibly reinforced by immersing in FeCl₃/HCl and pure water and softened by immersing in HCl. The tensile strength is 2.5 MPa with the break strain of 700%. Multiple shape memory capability is found depending on this unique feature, the hydrogel can be fixed in four temporary shapes by adjusting the immersing time in FeCl₃/HCl and pure water, and recovered in sequence by immersing in HCl. This hydrogel also exhibits perfect self‐healing behavior, the cut as‐prepared hydrogel is almost completely healed by immersing in FeCl₃/HCl. Besides, the hydrogel shows enhanced electrical conductivity with the presence of GO and Fe³⁺. This supertough hydrogel provides a new way to design soft actuators.

     

Bioinspired Tunable Sacrificial Bonds Endowing Tetra‐PEG Based PU Hydrogel with Tunable Mechanical Properties,Shape‐Memory,and Self‐Healing Functions

Development of hydrogels with excellent and tunable mechanical properties combining with multifunctions is an intriguing issue in material science and engineering. Herein, bioinspired tunable sacrificial bonds are introduced into the tetra‐poly(ethylene glycol) (PEG) based polyurethane (PU) (TP) network to afford a hydrogel with tunable mechanical properties, shape‐memory, and self‐healing functions. The mussel‐inspired compound of Lysine‐dopamine (LDA) is introduced into the network of TP hydrogel through polyurethane/polyurea chemistry to form LDA‐tetra‐PEG‐PU (LTP) hydrogel. As catechol groups in LDAs can intermolecularly interact with each other and can also coordinate with ferric ions with different coordination ratios, these physical interactions with different strengths in the afforded LTP hydrogel construct kinds of sequentially tuned sacrificial bonds. As a result, these sacrificial bonds preferentially rupture prior to the covalent network upon external loading, which dissipate the energy and endow the hydrogel with advanced and postadjustable mechanical properties. This mechanism is investigated in detail. Furthermore, the LTP hydrogel shows multifunctions such as shape‐memory and self‐healing abilities. In addition, the tetra‐PEG based hydrogel shows remarkable thermoresponsiveness that the hydrogel distinctly contracts with the increase of the temperature. The improved mechanical strength and multifunctions should enlarge the application areas of the tetra‐PEG based hydrogel in various fields.     

Transparent Surfactant/Epoxy Composite Coatings with Self‐Healing and Superhydrophilic Properties

In this paper, highly transparent, robust, and superhydrophilic polyethylene glycol tert‐octylphenyl ether nonionic surfactant/epoxy (Triton X‐100/epoxy, TXE) composite coatings are successfully prepared with a facile, one‐step drop‐casting method by mixing Triton X‐100 with an epoxy resin and an amine curing agent. The hydrogen bond reaction between the hydroxyl group of Triton X‐100 and the ether group of the epoxy resin improves the compatibility and reduces the glass transition temperature (T_g) of the TXE composite coatings. The free Triton X‐100 surfactant easily accumulates on the surface of the TXE composite coatings, which improves the hydrophilicity of the TXE composite coatings. The TXE composite coatings are self‐healable because of their low T_g and the migration of Triton X‐100 small molecule surfactant. Any damage arising from denting, cutting, or wiping by tetrahydrofuran can be healed, and the composite coating can regain its superhydrophilic properties through a heating process. The TXE composite coatings demonstrate excellent acid, alkali, salt, high temperature, and ultrasonic‐resistant properties. This facile preparation technique has the potential to be applied in the scalable fabrication of multifunctional coatings in anti‐fogging, oil–water separation, and optical–electric devices.     

Synthesis,Characterization, and Viscoelastic Behavior of Thermothickening Poly (N-Isopropylacrylamide-Methacrylicacide-Vinylpyrrolidone) Nanogels as an Injectable Biocompatible Drug Carrier

In the present work, the preparation of dual thermo-/pH-responsive nanogels composed poly (NIPAAm-MAA-VP) was investigated as an injectable carrier in which doxorubicin hydrochloride (DOX) was opted as an anticancer agent. The SEM photomicrographs showed that copolymer was almost spherical in shape with the mean diameter below 30 nm. Using dynamic oscillatory the gel-like behavior was observed at 37°C for the crosslinked polymer. Biocompatibility of the synthesized nanoparticles and superior antitumor activity of DOX-loaded nanoparticles were proved by in vitro cytotoxicity assay. The system is expected to be valuable for the delivery of chemotherapeutic agents in the treatment of solid tumors.     

A Self‐Healing PAM/CMHPG System for Unconventional Reservoir Stimulation

A hybrid chemically and physically linked polyacrylamide (PAM)/carboxymethyl hydroxypropyl guar gum (CMHPG) system is prepared via a fast and controllable one‐pot strategy. Due to the synergetic effect of the non‐covalent interactions between chains, these systems show improved, balanced mechanical properties. The apparent morphology, storage modulus G′, and loss modulus G″ show that these systems have rapid and almost full recovery ability (the self‐healing efficiency can reach 95%) with several hydrogen‐bonding interactions between two networks. This self‐healing property can cover the shortage of G′, G″, and viscosity loss at high shear force, which will help the system keep enough viscosity to create fractures or carry proppants during the whole fracturing process. Meanwhile, the self‐healing fracturing fluid can be broken easily and flow back to surface with little damage to the fracture conductivity, indicating great potential in unconventional reservoir which is sensitive to the fracturing fluid damage.     

Injectable and thermosensitive poly(organophosphazene) hydrogels for a 5‐fluorouracil delivery

The drug solubility and its release profiles of an anticancer drug from an injectable thermosensitive poly(organophosphazene) hydrogel bearing hydrophobic L ‐isoleucine ethyl ester and hydrophilic α‐amino‐ω‐methoxy‐poly(ethylene glycol) with and without hydrolysis‐sensitive glycyl lactate ethyl ester or functional glycyl glycine have been investigated. 5‐Fluorouracil (5‐FU) was used as a model anticancer drug. The aqueous solutions of 5‐FU incorporated poly(organophosphazenes) were an injectable fluid state at room temperature and formed a transparent gel at body temperature. The poly(organophosphazene) solution could enhance the solubility of 5‐FU and its solubility (34.26 mg/mL) was increased up to 10‐fold compared to that in phosphate‐buffered saline (3.39 mg/mL, pH 7.4, 4°C). The in vitro drug release profiles from poly(organophosphazene) hydrogels were established in phosphate‐buffered saline at pH 7.4 at 37°C and the release of 5‐FU was significantly affected by the diffusion‐controlled stage. The results suggest that the injectable and thermosensitive poly(organophosphazene) hydrogel is a potential carrier for 5‐FU to increase its solubility, control a relatively sustained and localized release at target sites and thus decrease systemic side effects. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Chamber/Capsule‐Integrated Self‐Healing Coating on Glass for Preventing Crack Propagation

A transparent self‐healing coating incorporating chambers and capsules capable of preventing the propagation of cracks in glass is presented. The main features simultaneously satisfy the requirements of high transmittance (≈90% in the visible region) and the ability to heal random and large‐area cracks in coated‐glass materials (up to 6 cm long, 20 µm wide, and 1 mm deep per chamber). Additionally, the polymerized hydrogel used as the healing agent can stop crack propagation because of its high mechanical strength and good adhesion to glass. Remarkably, the healed glass can withstand a force approximately four times greater than what can be withstood by the unhealed glass after cracking.