Mechanically Robust and Electrically Conductive Hybrid Hydrogel Electrolyte Enabled by Simultaneous Dual In Situ Sol-Gel Technique and Free Radical Copolymerization.

Mechanically robust and ionically conductive hydrogels poly(acrylamide-co-2-acrylamido-2-methylpropanesulfonate-lithium)/TiO2/SiO2 (P(AM-co-AMPSLi)/TiO2/SiO2) with inorganic hybrid crosslinking are fabricated through dual in situ sol-gel reaction of vinyltriethoxysilane (VTES) and tetrabutyl titanate (TBOT), and in situ radical copolymerization of acrylamide (AM), 2-acrylamide-2-methylpropanesulfonate-lithium (AMPSLi), and vinyl-SiO2. Due to the introduction of the sulfonic acid groups and Li+ by the reaction of AMPS with Li2CO3, the conductivity of the ionic hydrogel can reach 0.19 S m-1. Vinyl-SiO2 and nano-TiO2 are used in this hybrid hydrogel as both multifunctional hybrid crosslinkers and fillers. The hybrid hydrogels demonstrate high tensile strength (0.11-0.33 MPa) and elongation at break (98-1867%), ultrahigh compression strength (0.28-1.36 MPa), certain fatigue resistance, self-healing, and self-adhesive properties, which are due to covalent bonds between TiO2 and SiO2, as well as P(AM-co-AMPSLi) chains and SiO2, and noncovalent bonds between TiO2 and P(AM-co-AMPSLi) chains, as well as the organic frameworks. Furthermore, the specific capacitance, energy density, and power density of the supercapacitors based on ionic hybrid hydrogel electrolytes are 2.88 F g-1, 0.09 Wh kg-1, and 3.07 kW kg-1 at a current density of 0.05 A g-1, respectively. Consequently, the ionic hybrid hydrogels show great promise as flexible energy storage devices.

Molecular mechanism of abnormally large nonsoftening deformation in a tough hydrogel.

Tough soft materials usually show strain softening and inelastic deformation. Here, we study the molecular mechanism of abnormally large nonsoftening, quasi-linear but inelastic deformation in tough hydrogels made of hyperconnective physical network and linear polymers as molecular glues to the network. The interplay of hyperconnectivity of network and effective load transfer by molecular glues prevents stress concentration, which is revealed by an affine deformation of the network to the bulk deformation up to sample failure. The suppression of local stress concentration and strain amplification plays a key role in avoiding necking or strain softening and endows the gels with a unique large nonsoftening, quasi-linear but inelastic deformation.

Toughening Hydrogels by Forming Robust Hydrazide-Transition Metal Coordination Complexes.

Energy dissipation based on dynamic fracture of metal ligands is an effective way to toughen hydrogels for specific applications in biomedical and engineering fields. Exploration of new kinds of metal-ligand coordinates with robust bonding strength is crucial for the facile synthesis of tough gels. Here a hydrogel toughening strategy based on the formation of robust coordination complexes between the hydrazide ligands and zinc ions is reported. The resultant hydrogels exhibit high strength and toughness at room temperature. Their mechanical properties show temperature dependence due to the dynamic nature of coordination bonds. In addition, the amine group of hydrazides in the gel matrix provides a reactive site for Schiff's base reaction, enabling surface modification without influence on overall mechanical performances of the gel. The hydrazide ligands are easy to synthesize and can coordinate very well with several transition metals. Such a metal-ligand coordination should be suitable to develop tough soft materials with versatile applications.

Amphibious Polymer Materials with High Strength and Superb Toughness in Various Aquatic and Atmospheric Environments.

Herein, the fabrication of amphibious polymer materials with outstanding mechanical performances, both underwater and in the air is reported. A polyvinyl alcohol/poly(2-methoxyethylacrylate) (PVA/PMEA) composite with multiscale nanostructures is prepared by combining solvent exchange and thermal annealing strategies, which contributes to nanophase separation with rigid PVA-rich and soft PMEA-rich phases and high-density crystalline domains of PVA chains, respectively. Benefiting from the multiscale nanostructure, the PVA/PMEA hydrogel demonstrates excellent stability in harsh (such as acidic, alkaline, and saline) aqueous solutions, as well as superior mechanical behavior with a breaking strength of up to 34.8 MPa and toughness of up to 214.2 MJ m-3 . Dehydrating the PVA/PMEA hydrogel results in an extremely robust plastic with a breaking strength of 65.4 MPa and toughness of 430.9 MJ m-3 . This study provides a promising phase-structure engineering route for constructing high-performance polymer materials for complex load-bearing environments.

Tough, high conductivity pectin polysaccharide-based hydrogel for strain sensing and real-time information transmission.

Hydrogels from natural polymers are eco-friendly, biocompatible and adjustable for manufacturing wearable sensors. However, it is still challenging to prepare natural polymer hydrogel sensors with excellent properties (e.g., high conductivity). Here, we developed a physically cross-linked, highly conductive and multifunctional hydrogel (named PPTP) to address this challenge. The natural renewable pectin-based PPTP hydrogel is synthesized by introducing tannic acid (TA), calcium chloride (CaCl2), and sodium chloride (NaCl) into the pectin/polyvinyl alcohol (PVA) dual network structure. The hydrogel exhibits excellent characteristics, including unique tensile strength (2.6155 MPa), high electrical conductivity (7 S m-1), and high sensitivity (GF = 3.75). It is also recyclable, further enhancing its eco-friendly nature. The PPTP hydrogel can be used for monitoring human joint activities, as flexible electrodes for monitoring electrocardiogram (ECG) signals, and touchable screen pen for electronic skin. Moreover, when combined with Morse code and wireless Bluetooth technology, PPTP hydrogels can be used for underwater and land information encryption, and decryption. Our unique PPTP hydrogel offers promising opportunities for medical monitoring, information transfer, and human-computer interaction.

3D Printing of Tough Hydrogel Scaffolds with Functional Surface Structures for Tissue Regeneration.

Hydrogel scaffolds have numerous potential applications in the tissue engineering field. However, tough hydrogel scaffolds implanted in vivo are seldom reported because it is difficult to balance biocompatibility and high mechanical properties. Inspired by Chinese ramen, we propose a universal fabricating method (printing-P, training-T, cross-linking-C, PTC & PCT) for tough hydrogel scaffolds to fill this gap. First, 3D printing fabricates a hydrogel scaffold with desired structures (P). Then, the scaffold could have extraordinarily high mechanical properties and functional surface structure by cycle mechanical training with salting-out assistance (T). Finally, the training results are fixed by photo-cross-linking processing (C). The tough gelatin hydrogel scaffolds exhibit excellent tensile strength of 6.66 MPa (622-fold untreated) and have excellent biocompatibility. Furthermore, this scaffold possesses functional surface structures from nanometer to micron to millimeter, which can efficiently induce directional cell growth. Interestingly, this strategy can produce bionic human tissue with mechanical properties of 10 kPa-10 MPa by changing the type of salt, and many hydrogels, such as gelatin and silk, could be improved with PTC or PCT strategies. Animal experiments show that this scaffold can effectively promote the new generation of muscle fibers, blood vessels, and nerves within 4 weeks, prompting the rapid regeneration of large-volume muscle loss injuries.

A Glucose-Responsive Cannula for Automated and Electronics-Free Insulin Delivery.

Automated delivery of insulin based on continuous glucose monitoring is revolutionizing the way insulin-dependent diabetes is treated. However, challenges remain for the widespread adoption of these systems, including the requirement of a separate glucose sensor, sophisticated electronics and algorithms, and the need for significant user input to operate these costly therapies. Herein, a user-centric glucose-responsive cannula is reported for electronics-free insulin delivery. The cannula-made from a tough, elastomer-hydrogel hybrid membrane formed through a one-pot solvent exchange method-changes permeability to release insulin rapidly upon physiologically relevant varying glucose levels, providing simple and automated insulin delivery with no additional hardware or software. Two prototypes of the cannula are evaluated in insulin-deficient diabetic mice. The first cannula-an ends-sealed, subcutaneously inserted prototype-normalizes blood glucose levels for 3 d and controls postprandial glucose levels. The second, more translational version-a cannula with the distal end sealed and the proximal end connected to a transcutaneous injection port-likewise demonstrates tight, 3-d regulation of blood glucose levels when refilled twice daily. This proof-of-concept study may aid in the development of "smart" cannulas and next-generation insulin therapies at a reduced burden-of-care toll and cost to end-users.

High stretchable and tough xylan-g-gelatin hydrogel via the synergy of chemical cross-linking and salting out for strain sensors.

Stretchable and tough hydrogels have been extensively used in tissue engineering scaffolds and flexible electronics. However, it is still a significant challenge to prepare hydrogels with both tensile strength and toughness by utilizing xylan, which is abundant in nature. Herein, we present a novel hydrogel of carboxymethyl xylan(CMX) graft gelatin (G) and doped with conductive hydroxyl carbon nanotubes (OCNT). CMX and G are combined through amide bonding as well as intermolecular hydrogen bonding to form a semi-interpenetrating hydrogel network. The hydrogel was further subjected to salting-out treatment, which induced the aggregation of the CMX-g-G molecular chain and the formation of chain bundles to toughen the hydrogel, the tensile strain, tensile stress, and toughness of CMX-g-G hydrogels were 1.547 MPa, 324 %, and 2.31 MJ m-3, respectively. In addition, OCNT was used as a conductive filler to impart electrical conductivity and further improve the mechanical properties of CMX-g-G/OCNT hydrogel, and a tensile strength of 1.62 MPa was obtained. Thus, the synthesized CMX-g-G/OCNT hydrogel can be used as a reliable and sensitive strain sensor for monitoring human activity. This study opens up new horizons for the preparation of xylan-based high-performance hydrogels.

Construction of Tough Hydrogel Cross-Linked via Ionic Interaction by Protection Effect of Hydrophobic Domains.

Most hydrogels have poor mechanical properties, severely limiting their potential applications, and numerous approaches have been introduced to fabricate more robust and durable examples. However, these systems consist of nonbiodegradable polymers which limit their application in tissue engineering. Herein, we focus on the fabrication and investigate the influence of hydrophobic segments on ionic cross-linking properties for the construction of a tough, biodegradable hydrogel. A biodegradable, poly(γ-glutamic acid) polymer conjugated with a hydrophobic amino acid, l-phenylalanine ethyl ester (Phe), together with an ionic cross-linking group, alendronic acid (Aln) resulting in γ-PGA-Aln-Phe, was initially synthesized. Rheological assessments through time sweep oscillation testing revealed that the presence of hydrophobic domains accelerated gelation. Comparing gels with and without hydrophobic domains, the compressive strength of γ-PGA-Aln-Phe was found to be six times higher and exhibited longer stability properties in ethylenediaminetetraacetic acid solution, lasting for up to a month. Significantly, the contribution of the hydrophobic domains to the mechanical strength and stability of ionic cross-linking properties of the gel was found to be the dominant factor for the fabrication of a tough hydrogel. As a result, this study provides a new strategy for mechanical enhancement and preserves ionic cross-linked sites by the addition of hydrophobic domains. The development of tough, biodegradable hydrogels reported herein will open up new possibilities for applications in the field of biomaterials.

Magneto-Induced Janus Adhesive-Tough Hydrogels for Wearable Human Motion Sensing and Enhanced Low-Grade Heat Harvesting.

Janus hydrogels with different properties on the two surfaces have considerable potential in the field of material engineering applications. Various Janus hydrogels have been developed, but there are still some problems, such as stress mismatch caused by the double-layer structure and Janus failure caused by material diffusion in the gradient structure. Here, we report a Janus adhesive-tough hydrogel with polydopamine-decorated Fe3O4 nanoparticles (Fe3O4@PDA) at one side induced by magnetic field to avoid uncontrollable material diffusion in the cross-linking polymerization of acrylamide with alginate-calcium. The magneto-induced Janus (MIJ) hydrogel has an adhesive surface and a tough bulk without an obvious interface to avoid stress mismatch. Due to the intrinsic dissipative matrix and the abundant catechol groups on the adhesive surface, it shows strong adhesion onto various substrates. The MIJ hydrogel has high sensitivity (GF = 0.842) in detecting tiny human motion. Owing to the synergy of Fe3O4@PDA-enhanced interfacial adhesion and heat transfer, it is possible to quickly generate effective temperature differences when adhering to human skin. The MIJ hydrogel achieves a Seebeck coefficient of 13.01 mV·K-1 and an output power of 462.02 mW·m-2 at a 20 K temperature difference. This work proposes a novel strategy to construct Janus hydrogels for flexible wearable devices in human motion sensing and low-grade heat harvesting.

Growth of Double-Network Tough Hydrogel Coatings by Surface-Initiated Polymerization.

Hydrogel coatings exhibit versatile applications in biomedicine, flexible electronics, and environmental science. However, current coating methods encounter challenges in simultaneously achieving strong interfacial bonding, robust hydrogel coatings, and the ability to coat substrates with controlled thickness. This paper introduces a novel approach to grow a double-network (DN) tough hydrogel coating on various substrates. The process involves initial substrate modification using a silane coupling agent, followed by the deposition of an initiator layer on its surface. Subsequently, the substrate is immersed in a DN hydrogel precursor, where the coating grows under ultraviolet (UV) illumination. Precise control over the coating thickness is achieved by adjusting the UV illumination duration and the initiator quantity. The experimental measurement of adhesion reveals strong bonding between the DN hydrogel coating and diverse substrates, reaching up to 1012.9 J/m2 between the DN hydrogel coating and a glass substrate. The lubricity performance of the DN hydrogel coating is experimentally characterized, which is dependent on the coating thickness, applied pressure, and sliding velocity. The incorporation of 3D printing technology into the current coating method enables the creation of intricate hydrogel coating patterns on a flat substrate. Moreover, the hydrogel coating's versatility is demonstrated through its effective applications in oil-water separation and antifogging glasses, underscoring its wide-ranging potential. The robust DN hydrogel coating method presented here holds promise for advancing hydrogel applications across diverse fields.

Molecular design of an ultra-strong tissue adhesive hydrogel with tunable multifunctionality.

Designing adhesive hydrogels with optimal properties for the treatment of injured tissues is challenging due to the tradeoff between material stiffness and toughness while maintaining adherence to wet tissue surfaces. In most cases, bioadhesives with improved mechanical strength often lack an appropriate elastic compliance, hindering their application for sealing soft, elastic, and dynamic tissues. Here, we present a novel strategy for engineering tissue adhesives in which molecular building blocks are manipulated to allow for precise control and optimization of the various aforementioned properties without any tradeoffs. To introduce tunable mechanical properties and robust tissue adhesion, the hydrogel network presents different modes of covalent and noncovalent interactions using N-hydroxysuccinimide ester (NHS) conjugated alginate (Alg-NHS), poly (ethylene glycol) diacrylate (PEGDA), tannic acid (TA), and Fe3+ ions. Through combining and tuning different molecular interactions and a variety of crosslinking mechanisms, we were able to design an extremely elastic (924%) and tough (4697 kJ/m3) multifunctional hydrogel that could quickly adhere to wet tissue surfaces within 5 s of gentle pressing and deform to support physiological tissue function over time under wet conditions. While Alg-NHS provides covalent bonding with the tissue surfaces, the catechol moieties of TA molecules synergistically adopt a mussel-inspired adhesive mechanism to establish robust adherence to the wet tissue. The strong adhesion of the engineered bioadhesive patch is showcased by its application to rabbit conjunctiva and porcine cornea. Meanwhile, the engineered bioadhesive demonstrated painless detachable characteristics and in vitro biocompatibility. Additionally, due to the molecular interactions between TA and Fe3+, antioxidant and antibacterial properties required to support the wound healing pathways were also highlighted. Overall, by tuning various molecular interactions, we were able to develop a single-hydrogel platform with an "all-in-one" multifunctionality that can address current challenges of engineering hydrogel-based bioadhesives for tissue repair and sealing.

Specimen Geometry Effect on Experimental Tensile Mechanical Properties of Tough Hydrogels.

Synthetic tough hydrogels have received attention because they could mimic the mechanical properties of natural hydrogels, such as muscle, ligament, tendon, and cartilage. Many recent studies suggest various approaches to enhance the mechanical properties of tough hydrogels. However, directly comparing each hydrogel property in different reports is challenging because various testing specimen shapes/sizes were employed, affecting the experimental mechanical property values. This study demonstrates how the specimen geometry-the lengths and width of the reduced section-of a tough double-network hydrogel causes differences in experimental tensile mechanical values. In particular, the elastic modulus was systemically compared using eleven specimens of different shapes and sizes that were tensile tested, including a rectangle, ASTM D412-C and D412-D, JIS K6251-7, and seven customized dumbbell shapes with various lengths and widths of the reduced section. Unlike the rectangular specimen, which showed an inconsistent measurement of mechanical properties due to a local load concentration near the grip, dumbbell-shaped specimens exhibited a stable fracture at the reduced section. The dumbbell-shaped specimen with a shorter gauge length resulted in a smaller elastic modulus. Moreover, a relationship between the specimen dimension and measured elastic modulus value was derived, which allowed for the prediction of the experimental elastic modulus of dumbbell-shaped tough hydrogels with different dimensions. This study conveys a message that reminds the apparent experimental dependence of specimen geometry on the stress-strain measurement and the need to standardize the measurement of of numerous tough hydrogels for a fair comparison.

Eggshell membrane-incorporated cell friendly tough hydrogels with ultra-adhesive property.

Adhesive and tough hydrogels have received increased attention for their potential biomedical applications. However, traditional hydrogels have limited utility in tissue engineering because they tend to exhibit low biocompatibility, low adhesiveness, and poor mechanical properties. Herein, the use of the eggshell membrane (ESM) for developing tough, cell-friendly, and ultra-adhesive hydrogels is described. The ESM enhances the performance of the hydrogel network in three ways. First, its covalent cross-linking with the polyacrylamide and alginate chains strengthens the hydrogel network. Second, it provides functional groups, such as amine and carboxyl moieties, which are well known for enhancing the surface adhesion of biomaterials, thereby increasing the adhesiveness of the hydrogel. Third, it is a bioactive agent and improves cell adhesion and proliferation on the constructed scaffold. In conclusion, this study proposes the unique design of ESM-incorporated hydrogels with high toughness, cell-friendly, and ultra-adhesive properties for various biomedical engineering applications.

Strain-induced orientation facilitates the fabrication of highly stretchable and tough xylan-based hydrogel for strain sensors.

Stretchable and tough polysaccharide-based functional hydrogels have gained popularity for various applications. However, it still remains a great challenge to simultaneously own satisfactory stretchability and toughness, particularly when incorporating renewable xylan to offer sustainability. Herein, we describe a novel stretchable and tough xylan-based conductive hydrogel utilizing the natural feature of rosin derivative. The effect of different compositions on the mechanical properties and the physicochemical properties of corresponding xylan-based hydrogels were systematically investigated. Owing to the multiple non-covalent interactions among different components to dissipate energies and the strain-induced orientation of rosin derivative during the stretching, the highest tensile strength, strain, and toughness of xylan-based hydrogels could reach 0.34 MPa, 2098.4 %, and 3.79 ± 0.95 MJ/m3, respectively. Furthermore, by incorporating MXene as the conductive fillers, the strength and toughness of hydrogels were further enhanced to 0.51 MPa and 5.95 ± 1.19 MJ/m3. Finally, the synthesized xylan-based hydrogels were able to serve as a reliable and sensitive strain sensor to monitor the movements of human beings. This study provides new insights to develop stretchable and tough conductive xylan-based hydrogel, especially utilizing the natural feature of bio-based resources.

Tough Gelatin Hydrogel for Tissue Engineering.

Tough hydrogel has attracted considerable interest in various fields, however, due to poor biocompatibility, nondegradation, and pronounced compositional differences from natural tissues, it is difficult to be used for tissue regeneration. Here, a gelatin-based tough hydrogel (GBTH) is proposed to fill this gap. Inspired by human exercise to improve muscle strength, the synergistic effect is utilized to generate highly functional crystalline domains for resisting crack propagation. The GBTH exhibits excellent tensile strength of 6.67 MPa (145-fold that after untreated gelation). Furthermore, it is directly sutured to a ruptured tendon of adult rabbits due to its pronounced toughness and biocompatibility, self-degradability in vivo, and similarity to natural tissue components. Ruptured tendons can compensate for mechanotransduction by GBTH and stimulate tendon differentiation to quickly return to the initial state, that is, within eight weeks. This strategy provides a new avenue for preparation of highly biocompatible tough hydrogel for tissue regeneration.

Ultra-Tough Self-Healing Hydrogel via Hierarchical Energy Associative Dissipation.

Owing to high water content and homogeneous texture, conventional hydrogels hardly reach satisfactory mechanical performance. Tensile-resistant groups and structural heterogeneity are employed to fabricate tough hydrogels. However, those techniques significantly increase the complexity and cost of material synthesis, and have only limited applicability. Here, it is shown that ultra-tough hydrogels can be obtained via a unique hierarchical architecture composed of chemically coupled self-assembly units. The associative energy dissipation among them may be rationally engineered to yield libraries of tough gels with self-healing capability. Tunable tensile strength, fracture strain, and toughness of up to 19.6 MPa, 20 000%, and 135.7 MJ cm⁻3 are achieved, all of which exceed the best known records. The results demonstrate a universal strategy to prepare desired ultra-tough hydrogels in predictable and controllable manners.

Trifunctional Microgel-Mediated Preparation and Toughening of Printable High-Performance Chitosan Hydrogels for Underwater Communications.

Natural and biocompatible chitosan has demonstrated wide applications. However, rapidly fabricating high-performance chitosan hydrogels in one-step controllable processes is still a challenge for some advanced applications. Here, we report a trifunctional microgel-mediated photochemical (TMMP) strategy to achieve the fabrication of printable tough chitosan-based hydrogels (PTCHs) in seconds. Such microgels help the slow release of persulfate anions and their uniform dispersion in an aqueous solution of cationic chitosan. The released persulfates are available for preparing multiple networks of phenolic coupling of modified chitosan and radical polymerization of Pluronic F127 via orthogonal tris(bipyridine)ruthenium(II)-based photochemistry, respectively. Trifunctional microgels have reversible Ca2+-crosslinked networks that further improve the hydrogels' mechanical properties and toughness. The maximum stress and toughness increase by >20 folds compared to the chitosan and F127 hydrogels with single network structures. Moreover, these microgels enable the precursor to have a good shearing-thinning property and benefit the controllable preparation of PTCHs in a short time, as low as ∼4 s under visible light irradiation. It, therefore, is compatible with standard printing techniques to make complex structures. Strain sensors based on structured PTCHs have stable mechanical and responsive properties in the water, which are applied for real-time underwater communications (<0.4 s). It is anticipated that this one-step TMMP strategy opens new horizons for designing advanced chitosan hydrogels.

Skin-Inspired Ultra-Tough Supramolecular Multifunctional Hydrogel Electronic Skin for Human-Machine Interaction.

Multifunctional supramolecular ultra-tough bionic e-skin with unique durability for human-machine interaction in complex scenarios still remains challenging. Herein, we develop a skin-inspired ultra-tough e-skin with tunable mechanical properties by a physical cross-linking salting-freezing-thawing method. The gelling agent (ß-Glycerophosphate sodium: Gp) induces the aggregation and binding of PVA molecular chains and thereby toughens them (stress up to 5.79 MPa, toughness up to 13.96 MJ m-3). Notably, due to molecular self-assembly, hydrogels can be fully recycled and reprocessed by direct heating (100 °C for a few seconds), and the tensile strength can still be maintained at about 100% after six recoveries. The hydrogel integrates transparency (> 60%), super toughness (up to 13.96 MJ m-3, bearing 1500 times of its own tensile weight), good antibacterial properties (E. coli and S. aureus), UV protection (Filtration: 80%-90%), high electrical conductivity (4.72 S m-1), anti-swelling and recyclability. The hydrogel can not only monitor daily physiological activities, but also be used for complex activities underwater and message encryption/decryption. We also used it to create a complete finger joint rehabilitation system with an interactive interface that dynamically presents the user's health status. Our multifunctional electronic skin will have a profound impact on the future of new rehabilitation medical, human-machine interaction, VR/AR and the metaverse fields.

Printable Hydrogel Arrays for Portable and High-Throughput Shear-Mediated Assays.

Hydrogels have been widely used to entrap biomolecules for various biocatalytic reactions. However, solute diffusion in these matrices to initiate such reactions can be a very slow process. Conventional mixing remains a challenge as it can cause irreversible distortion or fragmentation of the hydrogel itself. To overcome the diffusion-limit, a shear-stress-mediated platform named the portable vortex-fluidic device (P-VFD) is developed. P-VFD is a portable platform which consists of two main components, (i) a plasma oxazoline-coated polyvinyl chloride (POx-PVC) film with polyacrylamide and alginate (PAAm/Alg-Ca2+) tough hydrogel covalently bound to its surface and (ii) a reactor tube (L × D: 90 mm × 20 mm) where the aforementioned POx-PVC film could be readily inserted for reactions. Through a spotting machine, the PAAm/Alg-Ca2+ hydrogel can be readily printed on a POx-PVC film in an array pattern and up to 25.4 J/m2 adhesion energy can be achieved. The hydrogel arrays on the film not only offer a strong matrix for entrapping biomolecules such as streptavidin-horseradish peroxidase but are also shear stress-tolerant in the reactor tube, enabling a >6-fold increase in its reaction rate after adding tetramethylbenzidine, relative to incubation. Through using the tough hydrogel and its stably bonded substrate, this portable platform effectively overcomes the diffusion-limit and achieves fast assay detection without causing appreciable hydrogel array deformation or dislocation on the substrate film.