Ionic Crosslinking Research Articles

Effects of Incorporating Ionic Crosslinking on 3D Printing of Biomass-Fungi Composite Materials.

Biomass-fungi composite materials primarily consist of biomass particles (sourced from agricultural residues) and a network of fungal hyphae that bind the biomass particles together. These materials have potential applications across diverse industries, such as packaging, furniture, and construction. 3D printing offers a new approach to manufacturing parts using biomass-fungi composite materials, as an alternative to traditional molding-based methods. However, there are challenges in producing parts with desired quality (for example, geometric accuracy after printing and height shrinkage several days after printing) by using 3D printing-based methods. This paper introduces an innovative approach to enhance part quality by incorporating ionic crosslinking into the 3D printing-based methods. While ionic crosslinking has been explored in hydrogel-based bioprinting, its application in biomass-fungi composite materials has not been reported. Using sodium alginate (SA) as the hydrogel and calcium chloride as the crosslinking agent, this paper investigates their effects on quality (geometric accuracy and height shrinkage) of 3D printed samples and physiochemical characteristics (rheological, chemical, and texture properties) of biomass-fungi composite materials. Results show that increasing SA concentration led to significant improvements in both geometric accuracy and height shrinkage of 3D printed samples. Moreover, crosslinking exposure significantly enhanced hardness of the biomass-fungi mixture samples prepared for texture profile analysis, while the inclusion of SA notably improved cohesiveness and springiness of the biomass-fungi mixture samples. Furthermore, Fourier transform infrared spectroscopy confirms the occurrence of ionic crosslinking within 3D printed samples. Results from this study can be used as a reference for developing new biomass-fungi mixtures for 3D printing in the future.

Development of large-scale laminar-structure nanofiltration membranes for high dye rejection and enhanced robustness: Utilizing potassium ion-crosslinked graphene oxide and polyethyleneimine surface coating

Laminar graphene oxide (GO) membranes are at the forefront of groundbreaking research as a prospective advanced solution for nanofiltration. Both physical and computational experiments have showcased the exceptional efficacy of these GO membranes. However, scalability and robustness issues still remain significant hurdles for the practical implementation of GO membranes. In this study, to address these issues concurrently, we employed tape-casting of GO hydrogel induced by potassium ion crosslinking alongside polyethyleneimine crosslinking between the tape-casted laminar GO layers and the porous support layer. Through this approach, we successfully crafted a scalable laminar GO membrane encompassing an area of 900 cm², characterized by good uniformity. The GO membranes achieved excellent rejection efficiencies of 99.22 %, 99.42 %, and 99.27 % for methylene blue, methyl orange, and rhodamine B, respectively, with 0.77 LMH/bar of pure water permeability. Furthermore, the GO membranes demonstrated enhanced stability, validated by both long-term operation and testing under harsh conditions.

Antibacterial sequential growth factor delivery from alginate/gelatin methacryloyl microspheres for bone regeneration

Autologous or allogeneic bone tissue grafts remain the mainstay of treatment for clinical bone defects. However, the risk of infection and donor scarcity in bone grafting pose challenges to the process. Therefore, the development of excellent biomaterial grafts is of great clinical importance for the repair of bone defects. In this study, we used gas-assisted microfluidics to construct double-cross-linked hydrogel microspheres with good biological function based on the ionic cross-linking of Cu2+ with alginate and photo-cross-linking of gelatin methacryloylamide (GelMA) by loading vascular endothelial growth factor (VEGF) and His-tagged bone morphogenetic protein-2 (BMP2) (AGMP@VEGF&BMP2). The Cu2+ component in the microspheres showed good antibacterial and drug-release behavior, whereas VEGF and BMP2 effectively promoted angiogenesis and bone tissue repair. In in vitro and in vivo experiments, the dual cross-linked hydrogel microspheres showed good biological function and biocompatibility. These results demonstrate that AGMP@VEGF&BMP2 microspheres could be used as a bone defect graft substitute to promote effective healing of bone defects and may be applied to other tissue engineering studies.

Zwitterion-functionalized nanofiber-based composite proton exchange membranes with superior ionic conductivity and chemical stability for direct methanol fuel cells

Proton exchange membranes with high ionic conductivity and good chemical stability are critical for achieving high power density and long lifespan of direct methanol cells (DMFCs). Herein, a zwitterionic molecule was grafted onto the surface of polyvinylidene fluoride (PVDF) nanofibers to obtain functionalized PVDF porous substrate (SBMA-PDA@PVDF). Then, sulfonated poly(ether ether ketone) (SPEEK) was filled into the pores of SBMA-PDA@PVDF, and further ionic cross-linked via H2SO4 to prepare the composite membrane (SBMA-PDA@PVDF/SPEEK). The basic groups on the zwitterionic interface could not only establish ionic cross-linking with SPEEK to increase chemical stability and reduce swelling, but also serve as the adsorption sites for subsequent H2SO4 cross-linking to significantly enhance proton conductivity. Super-high proton conductivity (165.34 mS cm−1, 80 °C) was achieved for the membrane, which was 2.12 times higher than that of the pure SPEEK. Moreover, the SBMA-PDA@PVDF/SPEEK membrane exhibited remarkably improved oxidative stability of 91.6 % mass retention after soaking in Fenton’s agent for 12 h, while pure SPEEK completely decomposed. Satisfactorily, the DMFC assembled with SBMA-PDA@PVDF/SPEEK exhibited a peak power density of 99.01 mW cm−2, which was twice as much as that of commercial Nafion 212 (48.88 mW cm−2). After 235 h durability test, only 11 % voltage loss was observed.

Ionic Crosslinked Hydrogel Films for Immediate Decontamination of Chemical Warfare Agents.

This study describes the development of hydrogel formulations with ionic crosslinking capacity and photocatalytic characteristics. The objective of this research is to provide an effective, accessible, "green", and facile route for the decontamination of chemical warfare agents (CWAs, namely the blistering agent-mustard gas/sulfur mustard (HD)) from contaminated surfaces, by decomposition and entrapment of CWAs and their degradation products inside the hydrogel films generated "on-site". The decontamination of the notorious warfare agent HD was successfully achieved through a dual hydrolytic-photocatalytic degradation process. Subsequently, the post-decontamination residues were encapsulated within a hydrogel membrane film produced via an ionic crosslinking mechanism. Polyvinyl alcohol (PVA) and sodium alginate (ALG) are the primary constituents of the decontaminating formulations. These polymeric components were chosen for this application due to their cost-effectiveness, versatility, and their ability to form hydrogen bonds, facilitating hydrogel formation. In the presence of divalent metallic ions, ALG undergoes ionic crosslinking, resulting in rapid gelation. This facilitated prompt PVA-ALG film curing and allowed for immediate decontamination of targeted surfaces. Additionally, bentonite nanoclay, titanium nanoparticles, and a tetrasulfonated nickel phthalocyanine (NiPc) derivative were incorporated into the formulations to enhance absorption capacity, improve mechanical properties, and confer photocatalytic activity to the hydrogels obtained via Zn2+-mediated ionic crosslinking. The resulting hydrogels underwent characterization using a variety of analytical techniques, including scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), viscometry, and mechanical analysis (shear, tensile, and compression tests), as well as swelling investigations, to establish the optimal formulations for CWA decontamination applications. The introduction of the fillers led to an increase in the maximum strain up to 0.14 MPa (maximum tensile resistance) and 0.39 MPa (maximum compressive stress). The UV-Vis characterization of the hydrogels allowed the determination of the band-gap value and absorption domain. A gas chromatography-mass spectrometry assay was employed to evaluate the decontamination efficacy for a chemical warfare agent (sulfur mustard-HD) and confirmed that the ionic crosslinked hydrogel films achieved decontamination efficiencies of up to 92.3%. Furthermore, the presence of the photocatalytic species can facilitate the degradation of up to 90% of the HD removed from the surface and entrapped inside the hydrogel matrix, which renders the post-decontamination residue significantly less dangerous.

High-Performance Monovalent Selective Cation Exchange Membranes with Ionically Cross-Linkable Side Chains: Effect of the Acidic Groups.

Inspired by the charge-governed protein channels located in the cell membrane, a series of polyether ether ketone-based polymers with side chains containing ionically cross-linkable quaternary ammonium groups and acidic groups have been designed and synthesized to prepare monovalent cation-selective membranes (MCEMs). Three acidic groups (sulfonic acid, carboxylic acid, and phenolic hydroxyl) with different acid dissociation constant (pKa) were selected to form the ionic cross-linking structure with quaternary ammonium groups in the membranes. The ionic cross-linking induced the nanophase separation and constructed ionic channels, which resulted in excellent mechanical performance and high cation fluxes. Interesting, the cation flux of membranes increased as the ionization of acidic groups increase, but the selectivity of MCEMs did not follow the same trend, which was mainly dependent on the affinity between the functional groups and the cations. Carboxyl group-containing MCEMs exhibited the best selectivity (9.01 for Li+/Mg2+), which was higher than that of the commercial monovalent cation-selective CIMS membrane. Therefore, it is possible to prepare stable MCEMs through a simple process using ionically cross-linkable polymers, and tuning acidic groups in the membranes provided an attractive approach to improving the cation flux and selectivity of MCEMs.

Optimizing alginate dressings with allantoin and chemical modifiers to promote wound healing

Wound healing requires diverse functionalities in dressings, and conventional materials often fall short in water absorption and moisture regulation. Natural sodium alginate is popular in wound dressings due to its excellent film-forming ability, biocompatibility, ionic crosslinking, and pH responsiveness. However, it has limitations in physical stability and solubility in aqueous environments. This study enhanced alginate dressings by incorporating allantoin and treating with calcium chloride and citric acid to improve physicochemical properties and mechanical performance. Treatments for S2 to S5 prevented dissociation and maintained integrity, with suitable water absorption (363 %–442 %) and water vapor transmission rates (612.53–715.39 g × m2 × day−1). The treatments also improved tensile strength (44.90–55.19 MPa). S2 had the highest migration ratio (52.71 %) of L929 cells and wound healing rates for mice skin (86.6 %), indicating that calcium chloride treatment is beneficial. All dressings (S1 to S5) exhibited low cytotoxicity against L929 cells and low hemolysis ratios, indicating good biocompatibility. Higher allantoin content improved wound healing efficacy. This study provides valuable insights for the design and development of alginate dressings in wound repair, expanding allantoin's application in wound healing.

Versatile synthesis of cellulose film with excellent electrothermal/photothermal dual responsiveness by introducing MXene and small molecule self-assembled nanosphere

Plant-derived biomaterials have great application prospects in solving environmental pollution and sustainable resource utilization, but the insufficient mechanical strength and lack of functional responsiveness often limit their further development. Inspired by natural small molecules functionalization, a vacuum-assisted filtration nanofibrillated cellulose (NFC)-based film with excellent antibacterial properties, mechanical strength, and electrothermal/photothermal dual-responsiveness was fabricated. As a natural bioactive molecule, antibacterial cinnamaldehyde (CA) is grafted onto tannic acid (TA) rich in pyrogallols via a small molecule self-assembly strategy, and then co-assembled with zinc acetate (ZA) through ion crosslinking to synthesize the functional TACA@ZA nanospheres. After incorporating the MXene and TACA@ZA, an inorganic-organic 3D network system was established in the NFC matrix through dynamic intermolecular hydrogen bonding and strong ionic cross-linking. The mechanical strength and toughness of hybrid composites are remarkably improved by 83.6 % and 418.9 %, respectively. Due to the synergistic effects of MXene and TACA@ZA, the designed NFC-based film also shows significantly enhanced antibacterial activity, UV-blocking ability, as well as photothermal and electrothermal performance. This bioinspired small molecule functionalization strategy opens an innovative design concept for the fabrication of multirole NFC-based biomaterials, which has great application prospects in the commercial fields of multifunctional adhesives, electronic devices, UV shielding coatings, and antibacterial materials.

Natural Polyelectrolyte Hydrogels with Two Types of Cross-Links with Different Energy

For the first time, gels of a polymer cross-linked by two types of ionic cross-links of different energies, namely trivalent chromium (III) ions and divalent iron (II) ions, were prepared. The negatively charged polysaccharide xanthan, a polyelectrolyte of natural origin, was used as a polymer. A study of xanthan gels cross-linked with each cross-linker separately was carried out to identify the optimal concentrations of each cross-linker for the production of a double cross-linked gel. The mechanical properties of hydrogels under oscillatory shear deformations were then studied. It was demonstrated that the simultaneous use of two cross-linkers resulted in a synergistic increase in the elastic modulus (plateau storage modulus) compared to gels cross-linked with each cross-linker separately. For a gel with two types of cross-links, the elastic modulus was 16 Pa. In contrast, for gels cross-linked with either chromium (III) cations or iron (II) cations, the elastic modulus was approximately 0.6 and 0.5 Pa, respectively. The strong effect can be attributed to the different nature of cross-linking between xanthan macromolecules and chromium (III) and iron (II) cations, as well as the different strength of the cross-links formed. The optimal range of pH values was determined in which a synergistic increase in the elastic modulus of gels with two types of cross-links was observed compared to the corresponding gels cross-linked with each cross-linker separately. Consequently, the concurrent utilisation of two cross-linking agents that generate cross-links with disparate energy levels represents an efficacious strategy to improve the tensile strength of polymer hydrogels.

Effect of halloysite nanotubes on the self-healing performance of natural rubber nanocomposites enabled by reversible zinc thiolate networks

This article presents the high loading halloysite nanotubes, Hals (20, 30, 40 and 50 phr) filled self-healing natural rubber nanocomposites crosslinked via ionic bonding networks. The reinforcing effect of high loading Hals on self-healing recovery and mechanical performance of NR were thoroughly examined and characterized by TEM, FT-IR, TGA, SEM, DMA, Anton Paar rheometer, and compression set analysis. It was observed that the high Hals content resulted in 100% improvement in tensile strength with an excellent healing recovery of up to 85% at room temperature without any external source. The reversible network structure formed via ionic crosslinks and its stability was identified by FTIR. TGA results revealed that the developed nanocomposites showed enhanced thermal stability compared to unfilled NR. Scanning Electron Microscopy (SEM) micrographs showed that the healed interfaces adhered well when the cut pieces were merged, suggesting that intermolecular diffusion occurred at the fractured surfaces. Overall, this study provides valuable insights into the reinforcing effects of Hals at higher loading on the structure and performance of self-healing natural rubber.

Soybean protein isolate-sodium alginate double network emulsion gels: Mechanism of formation and improved freeze-thaw stability

Soybean protein isolate (SPI) is widely used in the food industry. However, SPI-based emulsion gels tend to aggregate and undergo oiling-off during freeze-thawing. In this study, emulsion gels were prepared by a combination of heat treatment and ionic cross-linking using SPI and sodium alginate (SA) as raw materials. The focus was on exploring the mechanistic effects of the SPI-SA double network structure on the freeze-thaw stability of emulsion gels. The results showed that the addition of SA could form different types of network structures with SPI, due to different degrees of phase separation. In addition, SA appearing on the SPI network indicated that the addition of Ca2+ shielded the electrostatic repulsion between SPI and SA to form SPI-SA complexes. The disappearance of the characteristic peaks of SA and SPI in Fourier transform infrared spectroscopy analysis also confirmed this view. Low-field nuclear magnetic resonance data revealed that SA played a role in restricting water migration within the emulsion gels, increasing bound water content, and thereby improving the water-holding capacity of the emulsion gels. Therefore, the incorporation of SA improved the freeze-thaw stability of SPI emulsion gels. These findings offer a theoretical basis and technical support for SPI application in frozen products.

Impact of calcium-starch interactions on the textural and oil absorption properties of deep-fried potato mashes

The quality of mashed potato-based deep-fried products largely depends on their texture and oil content. In this study, Laser Ablation Inductively Coupled Plasma Mass Spectrometry analysis revealed that CaCl2 addition to the water used for blanching increased the presence of Ca2+ ions in potato cell walls, in the middle lamellae as well as in the cells. Potato mashes were softer and had lower storage and loss moduli when the CaCl2 concentration was increased. Similar observations were made for potato starch gels, highlighting the importance of the interactions between Ca2+ ions and starch for the properties of potato mashes. Interestingly, more amylose was extracted from potato starch gels when the system contained more CaCl2 due to increased amylose leaching from the granules and impaired crystallization. In contrast, amylopectin extraction yields were hardly affected. It is suggested that in potato mashes, the presence of more extracellular amylose with lower crystallinity changed the textural and rheological properties when CaCl2 was added to the blanching water. Additionally, Time Domain Proton Nuclear Magnetic Resonance revealed more and stronger interactions between starch and water in potato mashes due to Ca2+ ions cross-linking amylopectin. These stronger interactions are believed to contribute to the observed reduced oil absorption during deep-frying. Hence, CaCl2 addition during blanching can impact the quality of deep-fried potato mashes and holds promise to optimize the manufacture of frozen potato products.

Glassy gels toughened by solvent.

Glassy polymers are generally stiff and strong yet have limited extensibility1. By swelling with solvent, glassy polymers can become gels that are soft and weak yet have enhanced extensibility1-3. The marked changes in properties arise from the solvent increasing free volume between chains while weakening polymer-polymer interactions. Here we show that solvating polar polymers with ionic liquids (that is, ionogels4,5) at appropriate concentrations can produce a unique class of materials called glassy gels with desirable properties ofboth glasses and gels. The ionic liquid increases free volume and therefore extensibility despite the absence of conventional solvent (for example, water). Yet, the ionic liquid forms strong and abundant non-covalent crosslinks between polymer chains to render a stiff, tough, glassy, and homogeneous network (that is, no phase separation)6, at room temperature. Despite being more than 54 wt% liquid, the glassy gels exhibit enormous fracture strength (42 MPa), toughness (110 MJ m-3), yield strength (73 MPa) and Young's modulus (1 GPa). These values are similar to those of thermoplastics such as polyethylene, yet unlike thermoplastics, the glassy gels can be deformed up to 670% strain with full and rapid recovery on heating. These transparent materials form by a one-step polymerization and have impressive adhesive, self-healing and shape-memory properties.

Preparation and Characterization of Silica-Coated Sodium Alginate Hydrogel Beads and the Delivery of Curcumin

In this study, to address the defects of sodium alginate (SA), such as its susceptibility to disintegration, silica was coated on the outer layer of sodium alginate hydrogel beads in order to improve its swelling and slow-release properties. Tetraethyl orthosilicate (TEOS) was used as the hydrolyzed precursor, and the solution of silica precursor was prepared by sol-gel reaction under acidic conditions. Then SA–silica hydrogel beads prepared by ionic crosslinking method were immersed into the SiO2 precursor solution to prepare SA–silica hydrogel beads. The chemical structure and morphology of the hydrogel beads were characterized by XRD, FTIR, and SEM, and the results showed that the surface of SA–silica beads was successfully encapsulated with the outer layer of SiO2, and the surface was smooth and dense. The swelling experiments showed that the swelling performance effectively decreased with the increase of TEOS molar concentration, and the maximum swelling ratio of the hydrogel beads decreased from 41.07 to 14.3, and the time to reach the maximum swelling ratio was prolonged from 4 h to 8 h. The sustained-release experiments showed that the SA–silica hydrogel beads possessed a good pH sensitivity, and the time of sustained-release was significantly prolonged in vitro. Hemolysis and cytotoxicity experiments showed that the SA-silica hydrogel beads were biocompatible when the TEOS molar concentration was lower than 0.375 M. The SA–silica-2 hydrogel beads had good biocompatibility, swelling properties, and slow-release properties at the same time.

Colorimetric sensor to monitor the temperature with in situ synthesized silver nanoparticles embedded in carboxymethyl cellulose metallogel

A colorimetric sensing platform based on carboxymethyl cellulose-silver nanoparticles (CMC-AgNPs) metallogel was proposed to monitor the temperature history and quality of perishable products stored at low temperature. The carboxymethyl cellulose (CMC) metallogel, fabricated in the presence of Ag+, incorporates ionic crosslinking of biopolymers, complexation between reactants, and subsequent in situ synthesis of AgNPs, which are designed to lead the color transition of metallogel from colorless to dark brown depending on temperature and time. The mechanical and structural properties of metallogels and AgNPs were characterized by rheology, XRD, and FT-IR. Color changes associated with temperature, time, and metal ion precursors were examined by UV–visible spectroscopy and colorimetry. The longer the exposure time to thermal stress condition such as room temperature (25 °C) or high temperature (60 °C), the deeper the color of metallogel. The CMC-AgNPs metallogel-based sensor provides an efficient, safe way to track temperature history and assess perishable products’ quality, crucial for the safe distribution of food, vaccines, and medicines. This cost-effective and reliable visual sensor minimizes spoilage and health risks by enabling accurate temperature monitoring without the need for complicated equipment.

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.

Stepwise reinforcement strategy for guar gum/sodium alginate based films: Introduction of carboxylated cellulose nanofibers by different methods and further calcium ion crosslinking

Insufficient mechanical, barrier and water resistance properties of guar gum (GG) films limit their application in food packaging field. Herein, the properties of GG films were enhanced by a stepwise modification strategy. The mechanical and water vapor barrier properties of GG films were initially reinforced by doping with a different type of polysaccharide (sodium alginate; SA). Next, carboxylated cellulose nanofibers (CCN) were introduced as a reinforcing agent to improve film properties via two methods (blending and layer-by-layer (LBL) assembly method). Finally, the water resistance of composite films was further enhanced by calcium ion cross-linking treatment. GG/SA composite films exhibited better mechanical strength and water vapor barrier capacity compared to pristine GG film. In addition, the introduction of CCN, either by blending or LBL method, improved the light barrier, water vapor barrier and tensile strength. The calcium ion cross-linking treatment further enhanced the water vapor barrier, thermal stability, tensile strength and water resistance capacity. The potential applications of GG/SA/CCN films in real food packaging were also explored. In short, this study presents a simple and feasible performance enhancement strategy for GG and other underperforming polysaccharide matrix films, with potential applications in the development of high-performance bio-based food packaging materials.

Effects of Mineral Elements and Annealing on the Physicochemical Properties of Native Potato Starch

Native potato starch is an excellent carrier of minerals due to its inherent ion exchange capacity. Mineral enrichment not only changes the nutritional value but also influences starch pasting and swelling properties. Hydrothermal treatments like annealing constitute a straightforward and green way to tune functional properties. Here, novel combinations of mineral enrichment and annealing were studied. Ion exchange was readily achieved by suspending starch in a salt solution at room temperature over 3 h and confirmed by ICP-OES. Annealing at 50 °C for 24 h using demineralized water or salt solutions strongly affected pasting, thermal, and swelling properties. The obtained XRD and DSC results support a more ordered structure with relative crystallinity increasing from initially 41.7% to 44.4% and gelatinization onset temperature increasing from 60.39 to 65.94 J/g. Solid-state NMR spectroscopy revealed no detectable changes after annealing. Total digestible starch content decreased after annealing from 8.89 to 7.86 g/100 g. During both ion exchange at room temperature and annealing, monovalent cations promoted swelling and peak viscosity, and divalent cations suppressed peak viscosity through ionic crosslinking. The presented combination allows fine-tuning of pasting behavior, potentially enabling requirements of respective food applications to be met while offering an alternative to chemically modified starches.

Self-Evolving Hierarchical Hydrogel Fibers with Circadian Rhythms and Memory Functions.

The fusion of hierarchical tissues at interfaces, incorporating ultrafast selective transport channels, enables efficient matter exchange and energy transfer across multiscale structures in living organisms. However, achieving these characteristics simultaneously in an artificial multimaterial system is challenging. Here, this work presents a multimaterial hydrogel fiber with a hierarchical structure of interface fusion, which forms spontaneously through in situ hierarchy evolution induced by ionic cross-linking and molecular shear flow. Water transport occurs in the angstrom-scale confined slits created by aligned cellulose nanocrystals (CNCs) by direct Coulomb knock-on, resembling Newton's cradle motion. The fusion of interfaces enables high-efficiency water transport across multiscale layers, combined with Newton's cradle-like collective water motion, creating a highly sensitive negative feedback loop within the fiber. These fibers exhibit integrated behaviors of time-space perception, short-term memory and adaptive changes in shape. Additionally, they demonstrate rhythm characteristics, changing periodically in a 24-h day-night cycle. Composed of natural building blocks, these hierarchical hydrogel fibers exhibit a memristor effect similar to that of an elementary neuron, making them promising for applications in seamless on-skin and implantable bioelectronics.

Preparation of Cross-Linked Sodium Alginate Microspheres with Different Metal Ions Using the Microfluidic Electrospray Technology.

Microspheres are micrometer-sized particles that can load and gradually release drugs via physical encapsulation or adsorption onto the surface and within polymers. In the field of biomedicine, hydrogel microspheres have been extensively studied for their application as drug carriers owing to their ability to reduce the frequency of drug administration, minimize side effects, and improve patient compliance. Sodium alginate (ALG) is a naturally occurring linear polysaccharide with three backbone glycosidic linkages. There are two auxiliary hydroxyl groups present in each of the moieties of the polymer, which have the characteristics of an alcohol hydroxyl moiety. The synthetic ALG units can undergo chemical cross-linking reactions with metal ions, forming a cross-linked network structure of polymer stacks, ultimately forming a hydrogel. Hydrogel microspheres can be prepared using a simple process involving the ionic cross-linking properties of ALG. In this study, we prepared ALG-based hydrogel microspheres (ALGMS) using a microfluidic electrodeposition strategy. The prepared hydrogel microspheres were uniformly sized and well-dispersed, owing to accurate control of the microfluidic electrospray flow. ALGMS cross-linked with different metal ions were prepared using a microfluidic electrospray technique combining microfluidic and high electric field, and its antimicrobial properties, slow drug release ability, and biocompatibility were investigated. This technology holds promise for application in advanced drug development and production.