Coordination Crosslinking Research Articles

Coordination cross-linking of XNBR induced by different central ions

Coordination cross-linking of XNBR induced by different central ions

The role of multivalent cations in determining the cross-linking affinity of alginate hydrogels: A combined experimental and modeling study

This study explores the development of a comprehensive mathematical model to predict the cross-link density of alginate hydrogels using varying concentrations of divalent and trivalent ions. By systematically investigating the effects of Ca²⁺, Ba²⁺, Cu²⁺, Sr²⁺, Mg²⁺, Fe3⁺ and Al³⁺, the research describes the relationship between ion concentration and cross-link density. Experimental data reveals that the type and concentration of these ions critically influence the mechanical properties of the resulting hydrogels, with trivalent ions such as Fe³⁺ forming stronger, triple cross-links that significantly enhance the hydrogel's mechanical strength. Among the divalent ions, the trend in binding affinity is as follows: Ba²⁺ with the highest affinity followed by Sr²⁺, Ca²⁺ and Cu²⁺, while Mg²⁺ stands out with the lowest affinity, significantly differing from the others. The deviation of Cu²⁺ (transition metal ion) from the expected trend in ion interactions suggests that coordination chemistry, along with ionic radius, valence, and cation coordination abilities, plays a significant role in determining interaction strength with alginate. The proposed model, enhanced with fitting parameters k1 and k2 to account for ion-specific effects, leverages the unique binding affinities and coordination chemistry of each ion to tailor alginate hydrogels for specific applications. The parameter k1 reflects the affinity of the ions for the alginate chains, while k2 captures the coordination abilities and cross-linking efficiency. This work not only advances the understanding of ion-mediated cross-linking in alginate systems but also offers a valuable tool for the design and optimization of hydrogels with precise mechanical properties governed by various applications.

A photocurable ultra-tough eutectic gel with coordination crosslinking used for wearable sensors and TENG flexible electrodes

Flexible polymer molecular chains are of great interest to researchers in the field of flexible wearable electronics due to their unrivaled flexibility and ductility. However, achieving high toughness, high elasticity, environmental stability and easy machining of flexible electronic materials remains a challenge. In this study, we present a photocurable eutectic gel mainly composed of DMAPS, AAc, Zr4+ and deep eutectic solvents (DES). Due to the strong coordination between zirconium ions and polymer networks, the gel can be endowed with excellent properties, such as excellent tensile strength (1.14 MPa), low hysteresis (5 kJ·m−3) and good adhesion (above 40 kPa). DES can not only give the gel good electrical conductivity, but also maintain the stability of the gel to ensure that the leakage or volatilization of the solvent will not occur in use. The properties mentioned above allow the gel to achieve a sensitivity factor of up to 1.7 over a small strain range, demonstrating its potential applications in the field of flexible strain sensors and triboelectric flexible electrode materials. What’s more, the gel can be used to prepare complex geometric shapes with high precision through digital light processing (DLP) based 3D printing technology. Therefore, this work introduces a novel approach for the development of highly stable flexible wearable devices, which has the potential to expand the applications of eutectic gels.

Zr4+ and Al3+ coordinated cross-linked conductive collagen fibers/solvent-free polyurethane foam with ultra-low reflective electromagnetic shielding properties

In recent years, electromagnetic shielding materials with low reflectance have developed rapidly. However, high material cost, poor bonding fastness, weak mechanical properties and other problems seriously limit its effect in practical use. In this work, flexible conductive collagen fibers (CLF-Zr4+/Al3+-CNTs) were prepared using chromium tanned waste leather as ingredient, carbon nanotubes (CNTs) as conductive filler and transition metal ions as coordination crosslinking agents, and their molecular dynamics were investigated by quantum chemical simulation software. On this basis, a flexible conductive foam with the double layer and double core-clad structure containing carbon nanotubes was constructed using the solvent-free polyurethane (SFPU) chemical foaming technology, and their electromagnetic shielding properties and reflectance were studied. The experiment results showed that when the ratio of CLF-Zr4+/Al3+-CNTs to SFPU polyol is 1:9 and the impregnation times of CNTs are 2, the loading capacity of CNTs in conductive foam is 0.14 mg/cm3, the electrical conductivity is 57.8 S/m, and the thermal conductivity is 0.061 W/(m·K). Meanwhile, when the thickness is 3 cm, the electromagnetic shielding performance is 42.09 dB, and the reflection efficiency is 0.66 %, the lowest reflection efficiency reaches 0.16 % in the experiment. The mechanism of electromagnetic shielding in conductive foams with the double layer and double core-clad structure has been further explored. The experiment results proved that the flexible conductive foam has excellent mechanical properties, stability, heat insulation and flame retardant properties, and has excellent electromagnetic shielding and low reflection characteristics due to its abundant holes, functional group, interface and hierarchical structure.

Noncanonical Amino Acid Incorporation Modulates Condensate States of Intrinsically Disordered Proteins in Escherichia coli Cells.

Biomolecular condensates are distinct subcellular structures with on-demand material states and dynamics in living cells. However, strategies for modulating their material states and physicochemical properties are lacking. Here, we report a chemical strategy for modulating the condensate states of intrinsically disordered proteins in bacterial Escherichia coli cells. This is achieved by noncanonical amino acid (DOPA) incorporation into model resilin-like proteins (RLPs) to endow autonomous oxidative and coordinative cross-linking mechanisms. Biogenesis of spherical gel-like condensates is achieved upon heterologous expression of the DOPA-incorporated RLP in the cells at 30 °C. We reveal that liquid-liquid phase separation underlies the formation of liquid condensates, and this liquid-like state is metastable and its dynamics is compromised by the oxidative and coordinative cross-linkings that ultimately drive the liquid-to-gel transition. Therefore, this study has deepened our understanding of biomolecular condensation and offers a new chemical strategy to expand the landscape of condensation phenotypes of living cells.

Room temperature shape self-adjustable tough hydrogel based on multi-physical crosslinking

Room temperature shape adjustable hydrogels (rtSAH) can be (re)processed into different stable shapes at ambient conditions, making them appealing for various applications. However, elastomer-like and mechanically tough rtSAH is hard to obtain because of the elastic recovery force that prevents a deformed new shape from being fixed. Herein, we demonstrate a supramolecular elastic rtSAH having high tensile strength (2.6 MPa) and large strain at break (1770 %), whose network structure is designed to rely on a combination of strong and weak non-covalent interactions through three types of physical crosslinking: host–guest interaction, hydrogen bonding and coordination interaction. When deformed at room temperature and held in that state for sufficient time, the hydrogel adapts to a stable new shape while remaining elastic. The reconstruction of the dynamic Fe3+-carboxylate coordination interaction in the deformed hydrogel is the key to self-locking the new shape with stored elastic energy and enabling the shape memory function. Exposure the rtSAH to UV light or an acid solution disrupts the coordination crosslinking and allows the hydrogel to recover its initial shape. The demonstrated structural design represents an effective strategy to develop all-physically crosslinked shape memory hydrogels whose shapes can be reprocessed and self-locked at room-temperature.

Ultrarobust, Self-Healing Poly(urethane-urea) Elastomer with Superior Tensile Strength and Intrinsic Flame Retardancy Enabled by Coordination Cross-Linking.

Poly(urethane-urea) elastomers (PUUEs) have gained significant attention recently due to their growing demand in electronic skin, wearable electronic devices, and aerospace applications. The practical implementation of these elastomers necessitates many exceptional properties to ensure robust and safe utilization. However, achieving an optimal balance between high mechanical strength, good self-healing at moderate temperatures, and efficient flame retardancy for poly(urethane-urea) elastomers remains a formidable challenge. In this study, we incorporated metal coordination bonds and flame-retarding phosphinate groups into the design of poly(urethane-urea) simultaneously, resulting in a high-strength, self-healing, and flame-retardant elastomer, termed PNPU-2%Zn. Additional supramolecular cross-links and plasticizing effects of phosphinate-endowed PUUEs with relatively remarkable tensile strength (20.9 MPa), high elastic modulus (10.8 MPa), and exceptional self-healing efficiency (above 97%). Besides, PNPU-2%Zn possessed self-extinguishing characteristics with a limiting oxygen index (LOI) of 26.5%. Such an elastomer with superior properties can resist both mechanical fracture and fire hazards, providing insights into the development of robust and high-performance components for applications in wearable electronic devices.

High-Performance Polyimide CO2 Separation Membrane Prepared by Zn(II) Coordination Cross-Linking

High-Performance Polyimide CO₂ Separation Membrane Prepared by Zn(II) Coordination Cross-Linking

Water-resistant and barrier properties of poly(vinyl alcohol)/nanocellulose films enhanced by metal ion crosslinking

Polyvinyl alcohol (PVA) is a promising alternative to non-biodegradable flexible packaging materials, and nanocellulose is often used to enhance the properties of PVA films, but the composite films still have poor water resistance and barrier properties. To address this issue, iron ions (Fe3+) were introduced into PVA/cellulose nanofibrils (CNF) films, and Fe3+ formed coordination bonds with carboxyl and hydroxyl groups on the surface of CNF and PVA chains. Therefore, constructing a strong coordination crosslinking network within the film and improving the interfacial interaction between PVA and CNF. The water resistance, mechanical and barrier properties of the crosslinked films were significantly improved. Compared with the un-crosslinked film, the oxygen transmission rate (OTR) was decreased by up to 67 %, and the water swelling ratio was significantly reduced from 1085 % to 352 %. The tensile strength of the film with 1.5 wt% Fe3+ reached 41.93 MPa, which was 62 % higher than that of the un-crosslinked film. Furthermore, the composite film demonstrated good recyclability, almost recovering its original mechanical properties in two recycling tests. This simple and effective method for preparing water resistance and barrier films shows potential applications in flexible packaging areas.

A Double Network Composite Hydrogel with Self-Regulating Cu2+/Luteolin Release and Mechanical Modulation for Enhanced Wound Healing.

Designing adaptive and smart hydrogel wound dressings to meet specific needs across different stages of wound healing is crucial. Here, we present a composite hydrogel, GSC/PBE@Lut, that offers self-regulating release of cupric ions and luteolin and modulates mechanical properties to promote chronic wound healing. The double network hydrogel, GSC, is fabricated through photo-cross-linking of gelatin methacrylate, followed by Cu2+-alginate coordination cross-linking. On one hand, GSC allows for rapid Cu2+ release to eliminate bacteria in the acidic pH environment during inflammation and reduces the hydrogel's mechanical strength to minimize tissue trauma during early dressing changes. On the other hand, GSC enables slow Cu2+ release during the proliferation stage, promoting angiogenesis and biocompatibility. Furthermore, the inclusion of pH- and reactive oxygen species (ROS)-responsive luteolin nanoparticles (PBE@Lut) in the hydrogel matrix allows for controlled release of luteolin, offering antioxidant and anti-inflammatory effects and promoting anti-inflammatory macrophage polarization. In a murine model of Staphylococcus aureus infected wounds, GSC/PBE@Lut demonstrates exceptional therapeutic benefits in antibacterial, anti-inflammatory, angiogenic, and tissue regeneration. Overall, our results suggest that smart hydrogels with controlled bioactive agent release and mechanical modulation present a promising solution for treating chronic wounds.

Biocompatible and Biodegradable 3D Graphene/Collagen Fiber Hybrids for High-Performance Conductive Networks and Sensors.

Polymer-based flexible conductive materials are crucial for wearable electronics, electronic skin, and other smart materials. However, their development and commercial applications have been hampered by the lack of strain tolerance in the conductive network, poor bonding with polymers, discomfort during wear, and a lack of biocompatibility. This study utilized oil-tanned leather with a natural network structure, high toughness, and high tensile deformation recovery as a structural template. A graphene (Gr) conductive network was then constructed on the collagen network of the leather, with coordination cross-linking between Gr and collagen fibers through aluminum ions (Al3+). A new flexible conductive material (Al-GL) was then constructed. Molecular dynamics simulations and experimental validation revealed the existence of physical adsorption, hydrogen bonding adsorption, and ligand bonding between Al3+, Gr, and collagen fibers. Although we established that the binding sites between Al3+ and collagen fibers were primarily on carboxyl groups (-COOH), the mechanism of chemical bonding between Gr and collagen fibers remains unclear. The Al-GL composite exhibited a high shrinkage temperature (67.4 °C) and low electrical resistance (16.1 kΩ·sq-1), as well as good softness (9.33 mN), biocompatibility, biodegradability (<60 h), and air and moisture permeability. Furthermore, the incorporation of Al3+ resulted in a heightened Gr binding strength on Al-GL, and the resistance remained comparable following 1 h of water washing. The Al-GL sensor prepared by WPU encapsulation not only demonstrated highly sensitive responses to diverse motion signals of the human body but also retained a certain degree of response to external mechanical effects underwater. Additionally, the Al-GL-based triboelectric nanogenerator (Al-GL TENG) exhibited distinct response signals to different materials. The Al-GL prepared by the one-pot method proposed in this study offers a novel approach to combining functional nanofillers and substrate materials, providing a theoretical foundation for collagen fiber-based flexible conductive materials.

Nanocellulose-based cobalt(II) coordinated malonic acid hybrid aerogels exhibiting reversible thermochromism and moisture sensor properties

The emergence of sustainable polymers and technologies has led to the development of innovative materials with minimal carbon emissions which find extensive applications in wearable electronics, biomedical sensors, and Internet of Things (IoT)-based monitoring systems. Nanocellulose which can be generated from abundant biomass materials has been widely recognized as a sustainable alternative for a diverse range of applications due to its remarkable properties and eco-friendly nature. By making use of the unique and easily accessible coordination transformation property of Co(II) ions and associated visible light absorption changes, we report a novel Co(II) cation-incorporated nanocellulose/malonic acid hybrid aerogel material that exhibits reversible thermochromism induced by thermal stimulus in the presence of atmospheric moisture. This effect is accentuated by the highly porous nature of the nanocellulose aerogel material we have developed. Besides the reversible thermochromic property which Co(II) ions exhibit, the metal ions act as very efficient reinforcing units contributing significantly to the structural stability and rigidity of the hierarchical aerogels by coordinative cross-linking through carboxylate moieties present in the TEMPO-oxidized cellulose nanofibers (TCNF) and additionally adding malonic acid to provide sufficient COO− for cross-linking. Thorough characterization and detailed investigation of as-prepared hybrid aerogels was conducted to evaluate their overall properties including reversible thermochromism and moisture sensor behaviour. Further, an Android mobile-based application was developed to demonstrate the real-world application of the aerogels for atmospheric humidity sensing.

Constructing Self-Healing Polydimethylsiloxane through Molecular Structure Design and Metal Ion Bonding.

Self-healing polydimethylsiloxane (PDMS) has garnered significant attention due to its potential applications across various fields. In this study, a functionalized modification of PDMS containing di-aminos was initially conducted using 2,6-pyridinedicarbonyl chloride to synthesize pyridine-PDMS (Py-PDMS). Subsequently, rare earth metal europium ions (Eu3+) were incorporated into Py-PDMS. Due to the coordination interaction between Eu3+ and organic ligands, a coordination cross-linking network was created within the Py-PDMS matrix, resulting in the fabrication of Eu3+-Py-PDMS elastomer. At a molar ratio of Eu3+ to ligands of 1:1, the tensile strength of Eu3+-Py-PDMS reached 1.4 MPa, with a fracture elongation of 824%. Due to the dynamic reversibility of coordination bonds, Eu3+-Py-PDMS with a metal-to-ligand molar ratio of 1:2 exhibited varying self-healing efficiencies at different temperatures. Notably, after 4 h of repair at 60 °C, its self-healing efficiency reached nearly 100%. Furthermore, the gas barrier properties of Eu3+-Py-PDMS with a molar ratio of 1:1 was improved compared with that of Eu3+-Py-PDMS with a molar ratio of 1:1. This study provides an effective strategy for the design and fabrication of PDMS with high mechanical strength, high gas barrier properties, and exceptional self-healing efficiency.

Fe3+-induced coordination cross-linking gallic acid-carboxymethyl cellulose self-healing hydrogel

Self-healing hydrogel is a promising soft material for applications in wound dressings, drug delivery, tissue engineering, biomimetic electronic skin, and wearable electronic devices. However, it is a challenge to fabricate the self-healing hydrogels without external stimuli. Inspired by mussel, the metal-catechol complexes were introduced into the hydrogel systems to prepare the mussel-inspired hydrogels by regulating the gelation kinetics of Fe3+ crosslinkers with gallic acid (GA) in this research. The amine-functionalized carboxymethyl cellulose (CMC) was grafted with GA and then chelated with Fe3+ to form a multi-response system. The crosslinking of carboxymethyl cellulose-ethylenediamine-gallic acid (CEG) hydrogel was controlled by adjusting the pH to affect the iron coordination chemistry, which could enhance the self-healing properties and mechanical strength of hydrogels. In addition, the CEG hydrogel exhibited great antibacterial and antioxidant properties. And the CEG hydrogel could strongly adhere to the skin tissue. The adhesion strength of CEG hydrogel on pigskin was 11.44 kPa, which is higher than that of commercial wound dressings (∼5 kPa). Moreover, the thixotropy of the CEG hydrogel was confirmed with rheological test. In summary, it has great potential in the application field of wound dressing.

Highly Stretchable and Self-Healable Tough Polymer Elastomer through Dy3+ and Cu2+ Coordination Cross-Linking

Highly Stretchable and Self-Healable Tough Polymer Elastomer through Dy³⁺ and Cu²⁺ Coordination Cross-Linking

Doping proanthocyanidins into gel/zirconium hybrid hydrogel to reshape the microenvironment of diabetic wounds for healing acceleration

Infection and chronic inflammation caused by oxidative stress are major challenges in chronic wound healing. Preparing a simple, efficient hydrogel with reactive oxygen–scavenging properties for chronic wound repair is a promising strategy. Herein, we report an injectable, self-repairing hydrogel with antioxidant and antibacterial properties that can be used to regenerate diabetic wounds. Hydrogels are prepared by coordination crosslinking of gelatin (Gel), a natural biopolymer derived from collagen, with Zr4+. Because of the dynamic properties of metal ion coordination bonds and the bactericidal effect of Zr4+, the obtained coordination hydrogels exhibit self-healing, injectable, and antibacterial properties. The plant polyphenol “proanthocyanidins,” which has reactive oxygen–scavenging and anti-inflammatory effects, was simultaneously loaded into the coordination hydrogel during cross-linking. We obtained a versatile hydrogel that is easy to prepare, resistant to mechanical irritation, and antioxidant, and antibacterial in vitro. We further demonstrated that the injectable self-healing hydrogels could effectively repair diabetic skin wounds and accelerate collagen deposition and wound healing. This study shows that the multifunctional antioxidant hydrogel has great potential in developing multifunctional biomaterials for chronic wound healing.

Coordination crosslinks of epoxidized natural rubber with reactive zinc chloride

Coordination crosslinks of epoxidized natural rubber with reactive zinc chloride

Muscle-inspired anisotropic hydrogel strain sensors with ultra-strong mechanical properties and improved sensing capabilities for human motion detection and Morse code transmission

Combining superior mechanical and electrochemical capabilities into conductive hydrogel sensors has attracted considerable attention in the field of flexible electronics. However, traditional hydrogels with randomly oriented polymer networks often exhibit isotropic mechanical and electrical properties, whereas the magic of anisotropy is universal in nature. Inspired by the anisotropic structure-dependent properties of muscles, this study develops a general and simple method for fabricating anisotropic ultra-high strength conducting hydrogels via tensile remodeling followed by ion coordination crosslinking. Highly oriented polymer networks of anisotropic hydrogels greatly improve their mechanical and sensing capabilities. The tensile stress and conductivity of the PVA-PAA/Fe3+ hydrogels along the parallel direction are significantly increased to 47.26 MPa and 292.64 mS/m, which are considerably greater than that of the vertical-oriented hydrogels (12.42 MPa and 169.09 mS/m). Moreover, the gauge factors (GF) of the parallel-oriented hydrogels are higher than that of the vertical-oriented hydrogels, demonstrating enhanced strain sensing performance. Anisotropic hydrogel sensors can monitor various human movements in real-time and integrate with Morse code for information decoding and transmission. This research work is expected to accelerate the burgeoning pace of conductive hydrogel sensors in soft electronics.

Self-healing transparent ionogel polymerized by liquid metal for strain sensor

Flexible electronic devices, sensing human movement and monitoring physiological signals, might be useful for performing research in the area of intelligent detection. Gallium (Ga), a liquid metal (LM), is often used as a soft conductive material in the form of droplets because of its unique properties. Herein, a liquid metal-induced ionogel is synthesized by polymerizing acrylic acid (AA) with the existence of poly(diallyldimethylammonium chloride) (PDDA) and Ga droplets. In the system, the free radical formed from Ga oxidation process initiates the polymerization of AA. Meanwhile, the Ga3+ produced by Ga oxidation forms a coordination with the –COO− on PAA chains. The coordination crosslinking sites create slip when the gel is exposed to external force, increasing the stretchability (5000 %) of the ionogel. When the Ga droplets are completely oxidized to Ga3+, the gel changes from silvery gray to transparent (80 %). In addition, the ionic liquids and the electrostatic interactions within the network enable the resultant ionogel anti-dehydration (98 %) and self-healing performances in a wide temperature range (-20 ∼ 20 °C). The liquid metal-induced ionogel can be assembled into a flexible sensor with adequate sensitivity, rapid response time (240 ms), and cyclic stability, demonstrating human movement patterns with accuracy to keep track of physiological signs.

Research on composite municipal solid waste incineration bottom ash and granulated blast furnace slag based geopolymers with sodium alginate for sealing coal seam gas drainage boreholes

This study has created geopolymer sealing materials from sodium alginate (SA), granulated blast furnace slag (GBFS), and municipal solid waste incineration bottom ash (MSWI-BA) to see how well they can seal coal seam gas drainage boreholes. In comparison to ordinary cement sealing material (CSM) and neat MSWI-BA based geopolymer, composite geopolymer sealing material (SIG) with 0.1 wt% SA has the advantages of appropriate setting time, improved fluidity, and increased compressive strength. Additionally, SIG demonstrated a slight expansion that aids in maintaining the durability of the seal. However, when compared to neat geopolymer, the addition of sodium alginate increased porosity and permeability slightly, but not to levels higher than CSM. Based on the microstructural characterization, a mechanism for the formation of SIG with coordination crosslinking structure in the network of C-A-S-H and N-A-S-H gels was proposed. The created composite geopolymer material, which is based on MSWI-BA and GBFS, therefore, has a lot of potential for use as sealing materials in coal seam gas drainage boreholes.