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Conductive hydrogels have been increasingly employed to construct wearable mechanosensors due to their excellent mechanical flexibility close to that of soft tissues. In this work, piezoelectric hydrogels are prepared through free radical copolymerization of acrylamide (AM) and acrylonitrile (AN) and further utilized in assembling flexible wearable mechanosensors. Introduction of the polyacrylonitrile (PAN) component in the copolymers endows the hydrogels with excellent piezoelectric properties. Meanwhile, significant enhancement of mechanical properties has been accessed by forming dipole-dipole interactions, which results in a tensile strength of 0.51 MPa. Flexible wearable mechanosensors are fabricated by utilizing piezoelectric hydrogels as key signal converting materials. Self-powered piezoelectric pressure sensors are assembled with a sensitivity ( S ) of 0.2 V kPa -1 . Additionally, resistive strain sensors (gauge factor (GF): 0.84, strain range: 0-250%) and capacitive pressure sensors ( S : 0.23 kPa -1 , pressure range: 0-8 kPa) are fabricated by utilizing such hydrogels. These flexible wearable mechanosensors can monitor diverse body movements such as joint bending, walking, running, and stair climbing. This work is anticipated to offer promising soft materials for efficient mechanical-to-electrical signal conversion and provides new insights into the development of various wearable mechanosensors.

β-Cyclodextrin (β-CD) is often used as a drug carrier for biomedical materials due to its unique cavity structure. Herein, β-CD was modified by acryloyl chloride and further copolymerized with N -isopropylacrylamide (NIPAM) and acrylic acid (AA) to obtain PNIPAM -co- β-CD-AC. The results showed that the critical phase transition temperature of PNIPAM/β-CD-AC could be controlled at 19 °C, and the fast sol-gel phase transition was realized in 2-10 s. The hydrophobic drug carried in this hydrogel can constantly be released for more than 6 days at pH values (pH 5.5-8), and the duration may match the recovery of the wound. As a dressing hydrogel, its rapid gel formation and inversion as well as shear-thinning behavior prevent secondary wound damage. The β-CD-based hydrogel also has good biocompatibility and antioxidant properties, which provide a good potential choice for wound dressings, especially for exposed wounds in winter.

Recently, versatile hydrogels with multifunctionality have been widely developed with emerging applications as wearable and implantable devices. In this work, we reported novel versatile hydrogels by self-catalyzing the gelation of an interpenetrating polymer network consisting of acrylic acid (AA) monomers and GA-modified collagen (GCOL) in situ decorated silver nanoparticles (AgNPs). The resultant hydrogel, namely AgNP@GCOL/PAA, has many desirable features, including good mechanical properties (such as 123 kPa, 916%, and 1961 J m -2 for the fracture stress, strain and tearing energy) that match with those of animal skin, excellent self-healing performance, favorable conductivity and strain sensitivity as a flexible biosensor, and excellent antibacterial and anti-UV properties, as well as the strong adhesiveness on skin. Moreover, AgNP@GCOL/PAA showed excellent biocompatibility via in vitro cell culture. Remarkably, AgNP@GCOL/PAA displayed superior hemostatic properties with sharply decreasing blood loss for a mouse liver incision, closely related to its strong self-adhesion which produced anchoring strength to the bleeding site and thus formed a network barrier with liver tissue. This study provides new opportunities for the facile preparation of widely used multifunctional collagen-based hydrogels based on a simple pyrogallol-Ag system.

The development of intelligent and multifunctional hydrogels having photothermal properties, good mechanical properties, sustained drug release abilities with low burst release, antibacterial properties, and biocompatibility is highly desirable in the biomaterial field. Herein, mesoporous polydopamine (MPDA) nanoparticles wrapped with graphene oxide (GO) were physically cross-linked in cellulose nanofibril (CNF) hydrogel to obtain a novel MPDA@GO/CNF composite hydrogel for controllable drug release. MPDA nanoparticles exhibited a high drug loading ratio (up to 35 wt %) for tetracycline hydrochloride (TH). GO was used to encapsulate MPDA nanoparticles for extending the drug release time and reinforcing the physical strength of the obtained hydrogel. The mechanical strength of the as-fabricated MPDA@GO/CNF composite hydrogel was five times greater compared to that of the pure CNF hydrogel. Drug release experiments demonstrated that burst release behavior was significantly reduced by adding MPDA@GO. The drug release time of the MPDA@GO/CNF composite hydrogel was 3 times and 7.2 times longer than that of the polydopamine/CNF hydrogel and pure CNF hydrogel, respectively. The sustained and controlled drug release behaviors of the composite hydrogel were highly dependent on the proportion of MPDA and GO. Moreover, the rate of drug release could be accelerated by near-infrared (NIR) light irradiation and pH value change. The drug release kinetics of the as-prepared composite hydrogel was well described by the Korsmeyer-Peppas model, and the drug release mechanism of TH from the composite hydrogel was anomalous transport. Importantly, this carefully designed MPDA@GO/CNF composite hydrogel showed good biocompatibility through an in vitro cytotoxicity test. In particular, the toxicity of GO was well shielded by the CNF hydrogel. Therefore, this novel MPDA@GO/CNF composite hydrogel with an encapsulation structure for controllable drug release and toxicity shielding of GO could be used as a very promising controlled drug delivery carrier, which may have potential applications for chemical and physical therapies.

In this study, a carboxyl-modified cellulosic hydrogel was developed as the base material for wound dressings. ε-poly-l-lysine, a natural polyamide, was then covalently linked to the hydrogel through a bioconjugation reaction, which was confirmed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR). The antibacterial efficacy of the hydrogel was tested against two model bacteria, Staphylococcus aureus and Pseudomonas aeruginosa , two of the most commonly found bacteria in wound infections. Bacterial viability and biofilm formation after exposure of bacteria to the hydrogels were used as efficacy indicators. Live/Dead assay was used to measure the number of compromised bacteria using a confocal laser scanning microscope. The results show that the antibacterial hydrogel was able to kill approximately 99% of the exposed bacteria after 3 h of exposure. In addition, NIH/3T3 fibroblasts were used to study the biocompatibility of the developed hydrogels. Water-soluble tetrazolium salt (WST)-1 assay was used to measure the metabolic activity of the cells and Live/Dead assay was used to measure the viability of the cells after 24, 48, and 72 h. The developed antibacterial hydrogels are light weight, have a high water-uptake capacity, and show high biocompatibility with the model mammalian cells, which make them a promising candidate to be used for wound dressing applications.

Stretchable and compressible hydrogels based on natural polymers have received immense considerations for electronics. The feasibility of using pure natural polymer-based hydrogels could be improved if their mechanical behaviors satisfy the requirements of practical applications. Herein, we report highly stretchable (tensile strain ∼126%) and compressible (compression strain ∼80%) cellulose ionic hydrogels (CIHs) among pure natural polymer-based hydrogels including cellulose, chitin, and chitosan via chemical cross-linking based on free radical polymerization of allyl cellulose in NaOH/urea aqueous solution. In addition, the hydrogels have good transparency (transmittance of ∼89% at 550 nm) and ionic conductivity (∼0.16 mS cm -1 ) and can be worked at -20 °C without freezing and visual loss of transparency. Moreover, the CIHs can serve as reliable and stable strain sensors and have been successfully used to monitor human activities. Significantly, the various properties of hydrogel can be controlled through rationally adjusting the chemically cross-linked density. Our methodology will prove useful in developing the satisfied mechanical and transparent CIHs for a myriad of applications in flexible electronics.

In this work, we prepare guar gum-based supramolecular hydrogel through the formation of borate/didiol bonds. This dynamic and reversible noncovalent borate/didiol interaction is critical for the multifunctional properties of supramolecular hydrogel. The FT-IR and XRD analysis verified the existence of boronate ester interactions between borax and guar gum. Moreover, the viscoelastic and mechanical behaviors of the hydrogels with different guar gum concentrations showed that the storage modulus and compressive stress were highest at guar gum concentration of 2 wt %. Besides, due to the dynamic and reservable properties of boronate ester, these guar gum-based hydrogels had excellent self-healing property, outstanding reformable and injectable capability. In addition, hydrogels also exhibited reversible gel-sol transformations by the application of physicochemical stimuli such as thermal and pH value. The coupling of these multifunctional properties made from low-cost, environment friendly, and readily available materials could have potential applications in many biomedical areas in the future. We expect that this simple strategy of fabricating the self-healing guar gum hydrogels with multistimuli responsive properties may enrich the avenue in the exploration of multifunctional guar gum based hydrogels to expand their potential applications in various fields.

The current study aims to demonstrate the influence of the surface chemistry of wood-derived cellulose nanofibril (CNF) hydrogels on fibroblasts for tissue engineering applications. TEMPO-mediated oxidation or carboxymethylation pretreatments were employed to produce hydrogels with different surface chemistry. This study demonstrates the following: first, the gelation of CNF with cell culture medium and formation of stable hydrogels with improved rheological properties; second, the response of mouse fibroblasts cultured on the surface of the hydrogels or sandwiched within the materials with respect to cytotoxicity, cell attachment, proliferation, morphology, and migration. Indirect cytotoxicity tests showed no toxic effect of either hydrogel. The direct contact with the carboxymethylated hydrogel adversely influenced the morphology of the cells and limited their spreading, while typical morphology and spreading of cells were observed with the TEMPO-oxidized hydrogel. The porous fibrous structure may be a key to cell proliferation and migration in the hydrogels.

Tunable erosion of polymeric materials is an important aspect of tissue engineering for reasons that include cell infiltration, controlled release of therapeutic agents, and ultimately to tissue healing. In general, the biological response to proteinaceous polymeric hydrogels is favorable (e.g., minimal inflammatory response). However, unlike synthetic polymers, achieving tunable erosion with natural materials is a challenge. Keratins are a class of intermediate filament proteins that can be obtained from several sources, including human hair, and have gained increasing levels of use in tissue engineering applications. An important characteristic of keratin proteins is the presence of a large number of cysteine residues. Two classes of keratins with different chemical properties can be obtained by varying the extraction techniques: (1) keratose by oxidative extraction and (2) kerateine by reductive extraction. Cysteine residues of keratose are "capped" by sulfonic acid and are unable to form covalent cross-links upon hydration, whereas cysteine residues of kerateine remain as sulfhydryl groups and spontaneously form covalent disulfide cross-links. Here, we describe a straightforward approach to fabricate keratin hydrogels with tunable rates of erosion by mixing keratose and kerateine. SEM imaging and mechanical testing of freeze-dried materials showed similar pore diameters and compressive moduli, respectively, for each keratose-kerateine mixture formulation (∼1200 kPa for freeze-dried materials and ∼1.5 kPa for hydrogels). However, the elastic modulus (G') determined by rheology varied in proportion with the keratose-kerateine ratios, as did the rate of hydrogel erosion and the release rate of thiol from the hydrogels. The variation in keratose-kerateine ratios also led to tunable control over release rates of recombinant human insulin-like growth factor 1.

Stimulus-responsive hydrogels, which can undergo significant physicochemical changes in response to various physical or chemical stimuli, have drawn wide attention in many fields. In this study, novel photoresponsive hydrogels prepared by free radical copolymerization of xylan-type hemicellulose methacrylate with 4-[(4-acryloyloxyphenyl)azo]benzoic acid (AOPAB) were investigated, which showed multiresponsive behaviors to pH, water/ethanol alternating solutions, and light. The swelling ratios of the prepared hydrogels in distilled water decreased from 9.8 to 2.2 g/g with AOPAB content increase from 2% to 16%. The hydrogel displayed rapid swelling and deswelling performance in water and ethanol alternating solutions. Additionally, under UV irradiation the trans-conformation of azobenzene in the hydrogel would generally convert into the cis-conformation and resulted in the hydrophilic/hydrophobic balance variation of the hydrogel. Therefore, the hydrogel loaded with vitamin B12 (VB12) showed a higher drug cumulative release rate under UV irradiation than that without UV irradiation.

When grafted β-cyclodextrin is used as targeting sites, Pluronic polymers have been introduced on the surface of cellulose nanocrystals by means of inclusion interaction between β-cyclodextrin and hydrophobic segment of the polymer. Because of the steric stabilization effect, surface poly(ethylene glycol) chains facilitate the dispersion and compatibility of nanocrystals, which also enhance the loading levels of nanocrystals in the hydrogel system. Meanwhile, uncovered poly(ethylene glycol) segments render the participating inclusion of α-cyclodextrin for the architecture of in situ hydrogels. Surface grafting and inclusion reactions were proved by solid (13)C NMR and FTIR. Grafting efficiency of β-cyclodextrin and inclusion efficiency of Pluronic on the surface of nanocrystals were confirmed by UV spectroscopy and elemental analysis. A significant enhancement of the structural and thermal stability of in situ hydrogels with high loading levels of modified nanocrystals (>5.77 wt %) was observed by rheological analysis. Further study reveals the performance and behavior of hydrogels under a different pH environment. Finally, in situ hydrogels were used as drug carrier for in vitro release of doxorubicin and exhibit the behavior of prolonged drug release with special release kinetics.

Exploitation of biomaterials derived from renewable resources is an important approach to address environmental and resource problems in the world today. In this paper, novel ionic hydrogels based on xylan-rich hemicelluloses were prepared by free radical graft copolymerization of acrylic acid (AA) and xylan-rich hemicelluloses (XH) by using N,N-methylene-bis(acrylamide) (MBA) as cross-linker and ammonium persulfate/N,N,N',N'-tetramethylethylenediamine (APS/TMEDA) as redox initiator system. The network characteristics of the ionic hydrogels were investigated by Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM), as well as by determination of mechanical properties, swelling, and stimuli responses to pH, salts, and organic solvents. The results showed that an increase in the MBA/XH or AA/XH ratio resulted in higher cross-linking density of the network and thus decreased the swelling ratio. Expansion of the network hydrogels took place at high pH, whereas shrinkage occurred at low pH or in salt solutions as well as in organic solvents. The ionic hydrogels had high water adsorption capacity and showed rapid and multiple responses to pH, ions, and organic solvents, which may allow their use in several areas such as adsorption, separation, and drug release systems.

The adhesion of polyvinylamine to wet cellulose was significantly enhanced by the presence of pendant phenylboronic acid groups. It is proposed that adhesion results from boronate ester formation with cellulose at pH > 8. Experiments with phenol derivatized polyvinylamine gave low adhesion supporting the fact that the boronate moiety was responsible for strong adhesion to never-dried cellulose surfaces.