Search Results (44)

Bio-based ionic conductive hydrogels have attracted significant attention for use in wearable electronic sensors due to their inherent flexibility, ionic conductivity, and biocompatibility. However, achieving a balance between high ionic conductivity and mechanical robustness remains a significant challenge. In this study, we present a simple yet effective strategy for fabricating a polyelectrolyte–chitin double-network hydrogel (CAA) via the copolymerization of acrylamide (AM) and acrylic acid (AA) with chitin in an AlCl₃-ZnCl₂-H₂O ternary molten salt system. The synergistic interactions of dynamic metal ion coordination bonds and hydrogen bonding impart the CAA hydrogel with outstanding mechanical properties, including a fracture strain of 1765.5% and a toughness of 494.4 kJ/m³, alongside a high ionic conductivity of 1.557 S/m. Moreover, the hydrogel exhibits excellent thermal stability across a wide temperature range (−50 °C to 25 °C). When employed as a wearable sensor, the hydrogel demonstrates a rapid response time (<0.2 s), remarkable durability over 95 cycles with less than 5% resistance drift, and high sensitivity in detecting various human joint motions (e.g., finger, knee, and elbow bending). It presents a scalable strategy for biomass-derived flexible electronics that harmonizes mechanical robustness with electromechanical performance. Full article

Self-healing hydrogels hold promise for smart sensors in bioengineering and intelligent systems, yet balancing self-healing ability with mechanical strength remains challenging. In this study, a self-healing hydrogel exhibiting superior stretchability was developed by embedding a combination of hydrogen bonding and dynamic metal coordination interactions, introduced by modified fenugreek galactomannan, ferric ions, and lignin silver nanoparticles, into a covalent polyacrylic acid (PAA) matrix. Synergistic covalent and multiple non-covalent interactions enabled the hydrogel with high self-healing ability and enhanced mechanical property. In particular, due to the introduction of multiple energy dissipation mechanisms, particularly migrative dynamic metal coordination interactions, the hydrogel exhibited ultra-high stretchability of up to 2000%. Furthermore, with the incorporation of lignin silver nanoparticles and ferric ions, the hydrogel demonstrated excellent strain sensitivity (gauge factor ≈ 3.94), with stable and repeatable resistance signals. Assembled into a flexible strain sensor, it effectively detected subtle human motions and organ vibrations, and even replaced conductive rubber in gaming controllers for real-time inputs. This study provides a versatile strategy for designing multifunctional hydrogels for advanced sensing applications. Full article

Marine biofouling, the process of marine microorganisms, algae, and invertebrates attaching to and forming biofilms on ship hulls, underwater infrastructure, and marine equipment in ocean environments, severely impacts shipping and underwater operations by increasing fuel consumption, maintenance costs, and corrosion risks, and by threatening marine ecosystem stability via invasive species transport. This study reports the development of a hydrogel-metal-organic framework (MOF)-quorum sensing inhibitor (QSI) antifouling coating on 304 stainless steel (SS) substrates. Inspired by mussel adhesion, a hydrophilic bionic hydrogel was first constructed via metal ion coordination. The traditional metal ion source was replaced with a zeolitic imidazolate framework-8 (ZIF-8) loaded with 2-(5H)-furanone (HF, a QSI) without altering coating formation. Physicochemical characterization using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), the Brunauer–Emmett–Teller (BET) method, and the diffraction of x-rays (XRD) confirmed successful HF loading into ZIF-8 with intact crystal structures. Antifouling tests showed HF@ZIF-8 enhanced antibacterial inhibition against Staphylococcus aureus (97.28%) and Escherichia coli (>97%) and suppressed Chromobacterium violaceum CV026 pigment synthesis at 0.25 mg/mL (sub-growth concentration). The reconstructed PG/PVP/PEI/HF@ZIF-8 coating achieved 72.47% corrosion inhibition via synergistic anodic protection and physical shielding. This work provides a novel green approach for surface antifouling and drag reduction, highlighting MOF-loaded QSIs as promising additives to enhance the antifouling performance of hydrogel coatings, anti-corrosion performance, and QSI performance for sustainable marine engineering applications. Full article

Background/Objectives: A sustainable inflammatory response is a significant obstacle for diabetic wound care. In this study, the pH-sensitive multifunctional hydrogel ODex/BSA-Zn was fabricated via a Schiff base and coordination force for the first time. Methods: The hydrogel consisted of oxidized dextran (ODex), bovine serum albumin (BSA), and zinc ions (Zn²⁺) in the absence of an additional crosslinking agent. Results: The hydrogel showed excellent mechanical stability, fast self-healing ability, and significant anti-inflammatory effects, as demonstrated by the formation of dynamic covalent bonds between the aldehyde group (-CHO) of ODex and the amino group (-NH₂) of BSA via the Schiff base reaction, as well as the metal-ion coordination reaction of Zn²⁺ with the imidazole ring of BSA. In a diabetic mouse full-thickness cutaneous defect wound model, the ODex/BSA-Zn hydrogel could effectively inhibit the inflammatory response and increase collagen deposition, thereby accelerating the transition of macrophage M1 to M2 and promoting wound closure. This study offers a promising therapeutic approach for managing long-term diabetic ulcers. Full article

A series of stimuli-responsive fluorescent hydrogels were successfully synthesized via micelle radical copolymerization of hydrophilic acrylamide (AM), hydrophobic chromophore terpyridine-based monomer (TPY), and N-isopropylacrylamide (NIPAM). These hydrogels presented blue emissions (423–440 nm) under room temperature, which is caused by the π-π* transition of the conjugated structures. Once the ambient temperature was increased to 55 °C, the fluorescence color changed from blue (430 nm) to pink (575 nm) within 10 min, subsequently to yellow (535 nm), and eventually back to pink. The thermal-responsive properties are attributed to the transition of the TPY units from unimer to dimer aggregation via the intermolecular charge transfer complex at high temperatures. The hydrogels showed pH-responsive properties. The emission peak of the hydrogel exhibited a blue shift of ~54 nm from neuter conditions to acidic conditions, while a 6 nm red shift to an alkaline environment was observed. The hydrogels demonstrated an obvious change in fluorescence intensity and wavelength upon adding different metal ions, which is caused by the coordination between the terpyridine units incorporated on the backbones and the metal ions. As a consequence, the hydrogels presented a sharp quenching fluorescence interaction with Fe²⁺, Fe³⁺, Cu²⁺, Hg²⁺, Ni²⁺, and Co²⁺, while it exhibited an enhanced fluorescence intensity interaction with Sn²⁺, Cd²⁺, and Zn²⁺. The microstructural, mechanical, and rheological properties of these luminescent hydrogels have been systematically investigated. Full article

Metal-coordinated hydrogels are becoming increasingly popular in the biomedical field due to their unique properties. However, the mechanism behind gel forming involving metal ions is not yet fully understood. In this work, terahertz spectroscopy was used to investigate the role of interfacial water in the gelation process of copper ion-coordinated poly(vinyl alcohol) hydrogels. The results showed that the binding of copper ions could alter the interfacial hydration dynamics of the poly(vinyl alcohol) polymers. Combined with the results of differential scanning calorimetry (DSC), we propose a possible hydration layer-mediated mechanism for the formation of cooper ion-coordinated hydrogel during the freeze–thaw cycle. These results highlight the value of terahertz spectroscopy as a sensor for studying the hydration process in hydrogels and provide an important clue for understanding the mechanism of hydrogelation in ion-coordinated hydrogels. Full article

The removal of toxic heavy metal ions from wastewater is of great significance in the protection of the environment and human health. Poly(gamma-glutamic acid) (PGA) is a non-toxic, biodegradable, and highly water-soluble polymer possessing carboxyl and imino functional groups. Herein, water-insoluble PGA-based hydrogels were prepared, characterized, and investigated as heavy metal adsorbents. The prepared hydrogels were recyclable and exhibited good adsorption effects on heavy metal ions including Cu²⁺, Cr⁶⁺, and Zn²⁺. The effects of adsorption parameters including temperature, solution pH, initial concentration of metal ions, and contact time on the adsorption capacity of the hydrogel for Cu²⁺ were investigated. The adsorption was a spontaneous and exothermic process. The process followed the pseudo-first-order kinetic model and Langmuir isotherm model, implying a physical and monolayer adsorption. The adsorption mechanisms investigation exhibited that Cu²⁺ adsorbed on the hydrogel via electrostatic interactions with anionic carboxylate groups of PGA in addition to the coordination interactions with the –NH groups. Importantly, the PGA hydrogel exhibited good reusability and the adsorption capability for Cu²⁺ remained high after five consecutive cycles. The properties of PGA hydrogel make it a potential candidate material for heavy metal ion removal in wastewater treatment. Full article

A disposable electrochemical sensor based on silver nanoparticle-embedded cellulose hydrogel composites was developed for sensitive detection of sulfamethoxazole residues in meat samples. Scanning electron microscopy confirmed the porous structure of the cellulose matrix anchored with 20–50 nm silver nanoparticles (AgNPs). Fourier transform infrared spectroscopy and X-ray diffraction verified that the metallic AgNPs coordinated with the amorphous cellulose chains. At an optimum 0.5% loading, the nanocomposite sensor showed a peak-to-peak separation of 150 mV, diffusion-controlled charge transfer kinetics, and an electron transfer coefficient of 0.6 using a ferro/ferricyanide redox probe. Square-wave voltammetry was applied for sensing sulfamethoxazole based on its two-electron oxidation peak at 0.72 V vs. Ag/AgCl in Britton–Robinson buffer of pH 7.0. A linear detection range of 0.1–100 μM sulfamethoxazole was obtained with a sensitivity of 0.752 μA/μM and limit of detection of 0.04 μM. Successful recovery between 86 and 92% and less than 6% RSD was achieved from spiked meat samples. The key benefits of the proposed disposable sensor include facile fabrication, an antifouling surface, and a reliable quantification ability, meeting regulatory limits. This research demonstrates the potential of novel cellulose–silver nanocomposite materials towards developing rapid, low-cost electroanalytical devices for decentralized on-site screening of veterinary drug residues to ensure food safety. Full article

Hydrogels’ exceptional mechanical strength and skin-adhesion characteristics offer significant advantages for various applications, particularly in the fields of tissue adhesion and wearable sensors. Herein, we incorporated a combination of metal-coordination and hydrogen-bonding forces in the design of stretchable and adhesive hydrogels. We synthesized four hydrogels, namely PAID-0, PAID-1, PAID-2, and PAID-3, consisting of acrylamide (AAM), N,N′-methylene-bis-acrylamide (MBA), and methacrylic-modified dopamine (DA). The impact of different ratios of iron (III) ions to DA on each hydrogel’s performance was investigated. Our results demonstrate that the incorporation of iron–dopamine complexes significantly enhances the mechanical strength of the hydrogel. Interestingly, as the DA content increased, we observed a continuous and substantial improvement in both the stretchability and skin adhesiveness of the hydrogel. Among the hydrogels tested, PAID-3, which exhibited optimal mechanical properties, was selected for adhesion testing on various materials. Impressively, PAID-3 demonstrated excellent adhesion to diverse materials and, combined with the low cytotoxicity of PAID hydrogel, holds great promise as an innovative option for biomedical engineering applications. Full article

Nanocellulose hydrogels are a crucial category of soft biomaterials with versatile applications in tissue engineering, artificial extracellular matrices, and drug-delivery systems. In the present work, a simple and novel method, involving the self-assembly of cellulose nanocrystals (CNCs) induced by tannic acid (TA), was developed to construct a stable hydrogel (SH-CNC/TA) with oriented porous network structures. The gelation process is driven by the H-bonding interaction between the hydroxyl groups of CNCs and the catechol groups of TA, as substantiated by the atoms in molecules topology analysis and FTIR spectra. Interestingly, the assembled hydrogels exhibited a tunable hierarchical porous structure and mechanical moduli by varying the mass ratio of CNCs to TA. Furthermore, these hydrogels also demonstrate rapid self-healing ability due to the dynamic nature of the H-bond. Additionally, the structural stability of the SH-CNC/TA hydrogel could be further enhanced and adjusted by introducing coordination bonding between metal cations and TA. This H-bonding driven self-assembly method may promote the development of smart cellulose hydrogels with unique microstructures and properties for biomedical and other applications. Full article

Recently, many tough synthetic hydrogels have been created as promising candidates in fields such as smart electronic devices. In this paper, we propose a simple strategy to construct tough and robust hydrogels. Two-dimensional Ti₃C₂T_x MXene nanosheets and metal ions were introduced into poly(acrylamide-co-acrylic acid) hydrogels, the MXene nanosheets acted as multifunctional cross-linkers and effective stress-transfer centers, and physical cross-links were formed between Fe³⁺ and carboxylic acid. Under deformation, the coordination interactions exhibit reversible dissociation and reorganization properties, suggesting a novel mechanism of energy dissipation and stress redistribution. The design enabled the hydrogel to exhibit outstanding and balanced mechanical properties (tensile strength of up to 5.67 MPa and elongation at break of up to 508%). This study will facilitate the diverse applications of metallosupramolecular hydrogels. Full article

The development of biological macromolecule hydrogel dressings with fatigue resistance, sufficient mechanical strength, and versatility in clinical treatment is critical for accelerating full-thickness healing of skin wounds. Therefore, in this study, multifunctional, biological macromolecule hydrogels based on a recombinant type I collagen/chitosan scaffold incorporated with a metal–polyphenol structure were fabricated to accelerate wound healing. The resulting biological macromolecule hydrogel possesses sufficient mechanical strength, fatigue resistance, and healing properties, including antibacterial, antioxygenic, self-healing, vascularization, hemostatic, and adhesive abilities. Chitosan and recombinant type I collagen formed the scaffold network, which was the first covalent crosslinking network of the hydrogel. The second physical crosslinking network comprised the coordination of a metal–polyphenol structure, i.e., Cu²⁺ with the catechol group of dopamine methacrylamide (DMA) and stacking of DMA benzene rings. Double-crosslinked networks are interspersed and intertwined in the hydrogel to reduce the mechanical strength and increase its fatigue resistance, making it more suitable for clinical applications. Moreover, the biological macromolecule hydrogel can continuously release Cu²⁺, which provides strong antibacterial and vascularization properties. An in vivo full-thickness skin defect model confirmed that multifunctional, biological macromolecule hydrogels based on a recombinant type I collagen/chitosan scaffold incorporated with a metal–polyphenol structure can facilitate the formation of granulation tissue and collagen deposition for a short period to promote wound healing. This study highlights that this biological macromolecule hydrogel is a promising acute wound-healing dressing for biomedical applications. Full article

Metallogels represent a class of composite materials in which a metal can be a part of the gel network as a coordinated ion, act as a cross-linker, or be incorporated as metal nanoparticles in the gel matrix. Cellulose is a natural polymer that has a set of beneficial ecological, economic, and other properties that make it sustainable: wide availability, renewability of raw materials, low-cost, biocompatibility, and biodegradability. That is why metallogels based on cellulose hydrogels and additionally enriched with new properties delivered by metals offer exciting opportunities for advanced biomaterials. Cellulosic metallogels can be either transparent or opaque, which is determined by the nature of the raw materials for the hydrogel and the metal content in the metallogel. They also exhibit a variety of colors depending on the type of metal or its compounds. Due to the introduction of metals, the mechanical strength, thermal stability, and swelling ability of cellulosic materials are improved; however, in certain conditions, metal nanoparticles can deteriorate these characteristics. The embedding of metal into the hydrogel generally does not alter the supramolecular structure of the cellulose matrix, but the crystallinity index changes after decoration with metal particles. Metallogels containing silver (0), gold (0), and Zn(II) reveal antimicrobial and antiviral properties; in some cases, promotion of cell activity and proliferation are reported. The pore system of cellulose-based metallogels allows for a prolonged biocidal effect. Thus, the incorporation of metals into cellulose-based gels introduces unique properties and functionalities of this material. Full article

Polyampholyte (PA) hydrogels are randomly copolymerized from anionic and cationic monomers, showing good mechanical properties owing to the existence of numerous ionic bonds in the networks. However, relatively tough PA gels can be synthesized successfully only at high monomer concentrations (C_M), where relatively strong chain entanglements exist to stabilize the primary supramolecular networks. This study aims to toughen weak PA gels with relatively weak primary topological entanglements (at relatively low C_M) via a secondary equilibrium approach. According to this approach, an as-prepared PA gel is first dialyzed in a FeCl₃ solution to reach a swelling equilibrium and then dialyzed in sufficient deionized water to remove excess free ions to achieve a new equilibrium, resulting in the modified PA gels. It is proved that the modified PA gels are eventually constructed by both ionic and metal coordination bonds, which could synergistically enhance the chain interactions and enable the network toughening. Systematic studies indicate that both C_M and FeCl₃ concentration ($C_{{\mathrm{FeCl}}_3}$) influence the enhancement effectiveness of the modified PA gels, although all the gels could be dramatically enhanced. The mechanical properties of the modified PA gel could be optimized at C_M = 2.0 M and $C_{{\mathrm{FeCl}}_3}$ = 0.3 M, where the Young’s modulus, tensile fracture strength, and work of tension are improved by 1800%, 600%, and 820%, respectively, comparing to these of the original PA gel. By selecting a different PA gel system and diverse metal ions (i.e., Al³⁺, Mg²⁺, Ca²⁺), we further prove that the proposed approach is generally appliable. A theoretical model is used to understand the toughening mechanism. This work well extends the simple yet general approach for the toughening of weak PA gels with relatively weak chain entanglements. Full article

The de novo design and synthesis of peptide-based biocatalysts that can mimic the activity of natural enzymes is an exciting field with unique opportunities and challenges. In a natural enzyme, the active site is composed of an assembly of different amino acid residues, often coordinated with a metal ion. A metalloenzyme’s catalytic activity results from the dynamic and concerted interplay of various interactions among the residues and metal ions. Aiming to mimic such enzymes, simple peptide fragments, drawing structural inspiration from natural enzymes, can be utilized as a model. In our effort to mimic a metal-containing hydrolase, we designed peptide amphiphiles (PA) 1 and 2 with a terminal histidine having amide and acid functionalities, respectively, at its C-terminal, imparting differential ability to coordinate with Zn and Cu ions. The PAs demonstrate remarkable self-assembly behavior forming excellent nanofibers. Upon coordination with metal ions, depending on the coordination site the nanofibers become rigidified or weakened. Rheological studies revealed excellent mechanical properties of the hydrogels formed by the PAs and the PA–metal co-assemblies. Using such co-assemblies, we mimic hydrolase activity against a p-nitrophenyl acetate (p-NPA) substrate. Michaelis–Menten’s enzyme kinetic parameters indicated superior catalytic activity of 2 with Zn amongst all the assemblies. Full article