Boronate Ester Bonds Research Articles

A novel chitosan/quercetin-based film enables non-enzymatic detection of glucose: Electrochemical and fluorescent behavior

In this study, a novel functional hydrogel film was synthesized using natural polymer chitosan and quercetin as raw materials. Fourier transform infrared (FT-IR) spectra and X-ray photoelectron spectroscopy (XPS) analysis indicate that phenylboronic acid modified carbon nanodots (PBA-CDs) were successfully prepared via a simple microwave-assisted hydrothermal method. The experimental results demonstrate that a dual electrochemical and fluorescence detection of glucose can be realized based on the boronate ester bonding between chitosan/quercetin (Chit0/Quer) films and PBA-CDs. The addition of PBA-CDs hinders the electron transfer between the phenolic hydroxyl groups of quercetin and the redox mediators, and inhibits the intramolecular rotation of quercetin, which leads to a decreased electrical signal and enhanced fluorescence intensity. After the addition of glucose, the peak redox current of the Chit0/Quer hydrogel film is restored due to the competitive binding of glucose to the boronate ester, resulting in a dual-input logic circuit for the qualitative detection of glucose. In addition, the fluorescence intensity of the hydrogel decreases with increasing glucose concentration, and the concentration of glucose can be quantitatively detected by detecting the change in fluorescence intensity. Besides, the sensor has better stability and selectivity for biomarkers. Finally, we demonstrate that the electrochemical and fluorescence sensing strategies can be used for the detection of glucose in real beverage samples. In conclusion, based on the redox activity of quercetin and the competitive binding of boronate ester bonds, we explored a new strategy for enzyme-free electrochemical and fluorescence sensing for the detection of glucose, which is expected to be applied in biomedicine, food industry and other fields.

Nanotherapeutics-mediated restoration of pancreatic homeostasis and intestinal barrier for the treatment of severe acute pancreatitis.

Severe acute pancreatitis (SAP) is an inflammatory disease of the pancreas accompanied with intestinal injury, and effective therapeutic modalities are still highly lacking. Herein, a facile and effective nanotherapeutics (pHA@IBNCs) is developed to alleviate pancreatic inflammation and restore intestinal barrier for SAP treatment. Epigallocatechin gallate (EGCG, an anti-oxidant), interleukin-22 (IL-22, an anti-inflammatory and epithelial barrier-protecting cytokine), and bovine serum albumin (a framework protein), are assembled via non-covalent interactions to form nanocomplexes (IBNCs). Then, phenylboronic acid-modified hyaluronic acid (pHA) is synthesized and coated onto IBNCs via formation of the reversible boronate ester bonds to obtain pHA@IBNCs. Upon intravenous injection, pHA@IBNCs could efficiently accumulate at the lesion sites of sodium taurocholate (STC)-induced SAP mice, based on their prolonged blood circulation time and pHA-mediated targeting of activated intestinal epithelial cells and macrophages. Inside the inflammatory microenvironment, over-produced reactive oxygen species (ROS) trigger the shedding of the pHA layer and release of the drug payloads. Thereby, EGCG cooperates with IL-22 to attenuate pancreatitis and restore the intestinal barrier by scavenging ROS, suppressing pro-inflammatory cytokines secretion, and promoting the repair of intestinal epithelia. Such a nano-therapeutic approach targeting multiple pathological events may serve as a promising paradigm for the effective management of SAP.

Mechanically robust, self-healing and stretchable electromagnetic shielding materials based on multi-component dynamic bonded polyurethane elastomer

Stretchable self-healing electromagnetic interference (EMI) shielding materials can automatically restore their original performance after mechanical damage, and can still maintain over 20 dB EMI shielding effectiveness (EMI SE) under tensile state. In this work, a series of highly stretchable self-healing polyurethane elastomer PUBNS-X was prepared by introducing dynamic disulfide bonds, boronic ester bonds and boron-nitrogen coordination (B-N) on the polyurethane main chain. It was found that B-N coordination significantly increased the elongation at break and the tensile strength. The high dynamic reversibility of boronic ester, disulfide bond and B-N coordination bond synergistically endowed PUBNS-X with excellent temperature-triggered self-healing properties. The mechanical properties of PUBNS-X can be restored to more than 90 % at 60 °C. The pre-assembled silver nanowires (AgNWs) conductive network was then introduced into the polyurethane surface by taking advantage of the fluidity of the dynamically bonded polyurethane backbone to obtain a series of stretchable self-healing electromagnetic shielding composites (AgNWs/PUBNS-Y). The results showed that the EMI SE of AgNWs/PUBNS-Y can reach ∼55 dB, and the conductivity can be restored to 82 % of the original value after healing at 60 °C. The investigation of the electromagnetic interference shielding performance of composites under different strains showed that the EMI SE of AgNWs/PUBNS-3 can still maintain 20 dB under 90 % strain. These composites will have broad potential applications in the fields of flexible wearable electronic products, bionic intelligent materials and soft robots.

In-situ Forming Multipolymeric Glucose-Responsive Hydrogels.

Stimuli-responsive hydrogels (HGs) have shown promise for smart drug delivery applications. Specifically, glucose-responsive HGs having phenylboronic acid (PBA) functional groups are extensively pursued for insulin delivery in hyperglycemia. Current polymeric glucose-responsive HGs are cumbersome to fabricate and show a limited insulin release profile. Herein, we develop a straightforward fabrication of glucose-responsive multipolymer HGs (MPHGs) using a three-component in situ mixing. Molecular cargo, such as insulin, was loaded during the gelation. Heterobifunctional formylphenylboronic acid (FPBA) crosslinkers were used to interconnect polyvinyl alcohol (PVA) and branched polyethyleneimine (PEI) via boronate ester and imine bonds, respectively. Three positional isomers of FPBA (2FPBA, 3FPBA, and 4FPBA) resulted in HGs with distinct viscoelastic behaviors under the same conditions. HGs derived from 4FPBA exhibited more solid-like properties compared to 2FPBA and 3FPBA due to a higher crosslinking density. All the HGs exhibited glucose-responsive dissolution and release of embedded insulin cargo without disrupting the native structure. Insulin release profiles show a higher glucose-responsive release from 4FPBA-derived MPHGs. All the HGs were injectable, self-healing, and noncytotoxic below 10 μg/ml concentrations. The MPHGs developed in this study uncover new directions in creating glucose-responsive matrices for self-regulating drug delivery applications. In the future, detailed in vivo studies will be performed for clinical applications.

Adhesive lipophilic gels delivering rapamycin prevent oral leukoplakia from malignant transformation

Oral leukoplakia (OLK) is the most emblematic oral potentially malignant disorder that may precede the diagnosis of oral squamous cell carcinoma (OSCC) and has an overall malignant transformation rate of 9.8 %. Early intervention is crucial to reduce the malignant transformation rate from OLK to OSCC but the lack of effective local pharmaceutical preparations poses a challenge to clinical management. Rapamycin is speculated to prevent OLK from carcinogenesis and its inherent lipophilicity facilitates its penetration into stratum corneum. Nevertheless, hydrophilic hydrogels frequently encounter challenges when attempting to deliver lipophilic drugs. Furthermore, the oral cavity presents a complex environment defined by oral motor functions, saliva secretion cycles, dynamic fluctuations, and protective barriers comprising mucus and lipid layers. Consequently, addressing issues of muco-penetration and muco-adhesion is imperative for developing an effective drug delivery system aiming at delivering rapamycin to target oral potentially malignant disorders.Here, a dual-function hydrogel drug delivery system integrating adhesion and lipophilicity was successfully developed based on polyvinyl alcohol (PVA) and dioleoyl phosphatidylglycerol (DOPG) via dynamic boronic ester bonds. Rheological experiments based on orthogonal design revealed that PVA-DOPG hydrogels exhibited ideal adhesive strength (around 6 kPa) and could adhere to various surfaces in both dry and wet conditions. PVA-DOPG hydrogels also significantly promoted lipophilic molecules’ penetration into stratum corneum (integrated fluorescence density of 6.95 ± 0.52 × 106 and mean fluorescence depth of 0.96 ± 0.07 mm) of ex-vivo porcine buccal mucosa (p < 0.001). Furthermore, PVA-DOPG hydrogels incorporating rapamycin inhibited malignant transformation of OLK mouse model induced by 4-Nitroquinoline N-oxide (4-NQO), distinct improvements in survival (the neoplasm incidence density at the 40th day is 0.0091) (p < 0.05), decrease in neoplasm incidence density of 36.36 % and inhibition rate in neoplasm volume of 75.04 ± 33.67 % have been demonstrated, suggesting the hydrogels were valuable candidates for potential applications in the management of OLK.

ROS-responsive injectable hydrogels loaded with exosomes carrying miR-4500 reverse liver fibrosis

The reversal of liver fibrosis requires effective strategies to reduce oxidative stress and inhibition of hepatic stellate cell (HSC) activation. MiR-4500 regulates pathological angiogenesis and collagen mRNA stability, with the potential to inhibit fibrosis. Herein, we explored the inhibition of HSC activation in vitro by exosomes (Exos) carrying miR-4500 and encapsulated ExosmiR−4500 in an intelligent injectable hydrogel with biological activity and reactive oxygen species (ROS) responsiveness for application in oxidative stress environments. Briefly, reversible boronic ester bonds were integrated into gelatin-based hydrogels through dynamic crosslinking of quaternized chitosan (QCS) and 4-carboxyphenylboronic acid (CPBA)-modified gelatin. The QCS-CPBA-Gelatin (QCG) hydrogel scavenged excess ROS from the local microenvironment and released ExosmiR−4500 through the dissociation of boronic ester bonds, providing a favorable microenvironment and in situ sustained-release drug delivery system for ExosmiR−4500. The results showed that QCG@ExosmiR−4500 hydrogel has biocompatibility, biodegradability, and slow-release ability, which could effectively clear ROS and inhibit HSC activation and pathological angiogenesis in vitro and in vivo. Furthermore, transcriptome analysis suggests that the pharmacological mechanism of the QCG@ExosmiR−4500 hydrogel is mainly related to anti-oxidation, anti-angiogenesis, anti-fibrosis processes, and signaling pathways. Thus, our study demonstrates that an intelligently responsive ExosmiR−4500 delivery system based on injectable hydrogels is a promising strategy for the treatment of liver fibrosis.

Crosslinking of polyurethane with boronic ester bonds: An impact of B–N coordination

In this contribution, we reported a new approach to crosslink linear polyurethane (PU) with dynamic boronic ester bonds. First, a linear PU was synthesized, which carries a plethora of 1,3-diol structural units. Second, two structurally similar diboronic acids were designed and synthesized, which contained amino and amido groups, respectively. Thereafter, the crosslinking between the linear PU and the diboronic acids was carried out via the generation of boronic ester bonds. Thanks to the crosslinking, the PU networks significantly displayed improved thermomechanical properties, contingent on types of crosslinkers. More importantly, the excellent reprocessing and shape memory properties were imparted to the PU networks, which were implemented by dynamic boronic ester bonds between 1,3-diol moieties of the linear PU and boronic acids of the crosslinkers. The dynamic exchange of boronic ester bonds is responsible for the reprocessing properties. For the shape memory properties, the PU networks featured the reprogramming behavior of original shapes via the dynamic exchange of boronic ester bonds. More importantly, the shape memory properties were also dependent on types of diphenylboronic acids, which was reflected with the difference in dynamicity of boronic ester bonds. For the PU networks with amino-containing crosslinker, the boronic ester bonds featured the B–N coordination. As a result, the boronic ester bonds had the increased dynamicity, which significantly affected the reprocessing properties.

Dynamic Covalent Bonds Enabled Carbon Fiber Reinforced Polymers Recyclability and Material Circularity.

Due to their remarkable features of lightweight, high strength, stiffness, high-temperature resistance, and corrosion resistance, carbon fiber reinforced polymers (CFRPs) are extensively used in sports equipment, vehicles, aircraft, windmill blades, and other sectors. The urging need to develop a resource-saving and environmentally responsible society requires the recycling of CFRPs. Traditional CFRPs, on the other hand, are difficult to recycle due to the permanent covalent crosslinking of polymer matrices. The combination of covalent adaptable networks (CANs) with carbon fibers (CFs) marks a new development path for closed-loop recyclable CFRPs and polymer resins. In this review, we summarize the most recent developments of closed-loop recyclable CFRPs from the unique paradigm of dynamic crosslinking polymers, CANs. These sophisticated materials with diverse functions, oriented towards CFs recycling and resin sustainability, are further categorized into several active domains of dynamic covalent bonds, including ester bonds, imine bonds, disulfide bonds, boronic ester bonds, and acetal linkages, etc. Finally, the possible strategies for the future design of recyclable CFPRs by combining dynamic covalent chemistry innovation with materials interface science are proposed.

An Advanced Hydrogel Dressing System with Progressive Delivery and Layer-to-Layer Response for Diabetic Wound Healing

Wound healing in diabetic patients presents a significant challenge due to delayed inflammatory responses, which obstruct subsequent healing stages. In response, we have developed a progressive, layer-by-layer responsive hydrogel, specifically designed to meet the dynamic requirements of diabetic wounds throughout different healing phases. This hydrogel initiates with a glucose-responsive layer formed by boronate ester bonds between 4-arm-poly (ethylene glycol) succinimidyl glutarate (4arm-PEG-SG) and 3-aminophenylboronic acid. This configuration ensures precise control over the physicochemical properties, facilitating accurate drug release during the healing process. Furthermore, we have incorporated an active pharmaceutical ingredient ionic liquid (API) composed of diclofenac and L-carnitine. This combination effectively tackles the solubility and stability issues commonly associated with anti-inflammatory drugs. To further refine drug release, we integrated matrix metalloproteinase-9 (MMP-9)-sensitive gelatin microcapsules, ensuring a controlled release and preventing the abrupt, uneven drug distribution often seen in other systems. Our hydrogel's rheological properties closely resemble human skin, offering a more harmonious approach to diabetic wound healing. Overall, this progressive layer-by-layer responsive wound management system, which is a safe, efficient, and intelligent approach, holds significant potential for the clinical treatment of diabetic wounds. Statement of SignificanceThe two main problems of diabetic wounds are the long-term infiltration of inflammation and the delayed repair process. In this experiment, a glucose-responsive hierarchical drug delivery system was designed to intelligently adjust gel properties to meet the needs of inflammation and repair stage of wound healing, accelerate the transformation of inflammation and repair stage, and accelerate the process of repair stage. In addition, in order to achieve accurate drug release in anti-inflammatory layer hydrogels and avoid sudden drug release due to poor solubility of anti-inflammatory small molecule drugs, we constructed a ionic liquid of active pharmaceutical ingredients (API-ILs) using diclofenac and L-carnitine as raw materials. It was wrapped in MMP-9 enzyme active gelatin microcapsule to construct a double-reaction anti-inflammatory layer gel to achieve accurate drug release. These findings highlight the potential of our system in treating diabetic wounds, providing a significant advance in wound treatment.

Multi-touch microcapsules/silicone-polyacrylate hybrid hydrogels with precise self-healing ability and their self-powered sensing applications in emergency rescue

Hydrogels offer significant potential for use in wearable soft electronic devices. However, their application faces considerable challenges in outdoor emergencies or extreme environments where a power supply is unavailable. In this study, multi-touch microcapsules with phase change properties were prepared by coating nanogold through silica as Pickering particles. Subsequently, the microspheres were integrated into a silicone oil-modified polyacrylate hydrogel with self-healing capabilities, resulting in the fabrication of a hydrogel strain sensor that exhibits precise self-healing and self-powered functionality. The mechanical properties of the hydrogel sensor can be modified by adjusting the polymer composition. Due to the multi-contact structure of nano-gold on the surface of microcapsules and the dynamic boronic ester bond interaction, the hydrogel sensor possesses precision self-healing capability. In addition, the hydrogel sensors demonstrate high sensitivity, which can accurately detect some subtle human motions, such as joint flexion. Importantly, the synthesized composite hydrogel exhibits self-powered performance, which could be helpful for rescue operations in outdoor or extreme environments. This study provides helpful results that can be used in the development of wearable soft electronics based on conductive hydrogels.

Phosphorus/boron-containing, flame-retardant polyurethane elastomers with great mechanical, shape-memory, and recycling performances

Based on sustainable development strategy and practical application requirement, it is crucial to develop high-strength, recyclable, and flame-retardant polyurethane (PU) elastomers. Hence, a flame-retardant, reprocessable, high-performance polyurethane elastomer (PU-DP 1–7) with dynamic boronic ester bonds and phosphorus-containing groups was well-designed and prepared. The chemical structure of PU-DP 1–7 was confirmed by Fourier transform infrared spectrometry (FTIR) and X-ray photoelectron spectroscopy (XPS). PU-DP 1–7 shows a transmittance of about 60 % at the wavelength of 900 nm, and phosphorus and boron elements are evenly distributed within its surface, confirming the formation of uniform cross-linking network. The inclusion of phosphorus-and boron-containing groups endows PU-DP 1–7 with a vertical combustion (UL-94) V-0 rating, indicative of desired flame retardancy. In addition, PU-DP 1–7 exhibits a tensile strength of 42.7 MPa and an elongation at break of 616.9 %, with high adhesion strengths towards various substrates due to abundant hydrogen bonds within its network. Furthermore, the dynamic borate ester bonds endow PU-DP 1–7 with superior physical recycling and shape-memory properties. After hot-pressing at 130 °C, the reformed PU-DP 1–7 film shows an 83.6 % recovery efficiency in terms of elongation at break. This work presents an integrated strategy to create flame-retardant, recyclable polyurethane elastomers with great mechanical and shape-memory performances by introducing phosphorus-containing segments and dynamic boronic ester bonds.

Design of super stretchability, rapid self-healing, and self-adhesion hydrogel based on starch for wearable strain sensors

Since hydrogels are conductive, easily engineered, and sufficiently flexible to imitate the mechanical properties of human skin, they are seen as potential options for wearable strain sensors. However, it is still a great challenge to prepare a hydrogel through simple and straightforward methods that integrate excellent stretchability, ionic conductivity, toughness, self-adhesion, and self-healing. Herein, an acrylamide/3-acrylamide phenylboronic acid cross-linked network is modified to produce a semi-interpenetrating cross-linked hydrogel in just one easy step by adding starch. The prepared hydrogel contains dynamic boronic ester bonds and hydrogen bonds, which endow the exceptional stretchability (5769–13,976 %, 20–50 wt%), ideal transmittance (>90 %), self-adhesiveness (0.636 ± 0.060 kPa, 30 wt%), and self-healing properties. Notably, the self-healing process is completed instantly, achieving a healing strength of up to 81.21 %. Additionally, the aforementioned hydrogel exhibits a broad working strain range (≈ 500 %) and high sensitivity (gauge factor = 1.99) as a strain sensor, allowing it to record and track human actions precisely. This work provides a novel approach to synthesizing hydrogels with optimal overall mechanical characteristics, with the potential to facilitate the development of wearable strain sensing system based on hydrogels for real-world applications.

A multifunctional hydrogel dressing loaded with antibiotics for healing of infected wound

Wound bacterial infections can significantly delay the healing process and even lead to fetal sepsis. There is a need for multifunctional dressings that possess antibacterial property, tissue adhesive property, self-healing capability, and biocompatibility to effectively treat bacteria-infected wound. In this study, we report a dual dynamically crosslinked hydrogel, OHA-PBA/PVA/Gen, which incorporates the antibiotic gentamicin (Gen) as a dynamic crosslinker. The hydrogel is formed through the formation of Schiff base bonds between phenylboronic acid-grafted oxidized hyaluronic acid (OHA-PBA) and Gen, as well as boronic acid ester bonds between OHA-PBA and polyvinyl alcohol (PVA). This unique composition imparts tissue adhesiveness, injectability and self-healing property to the hydrogel. The hydrogel also exhibits pH-responsive antibiotic release behavior due to the acid-responsive dissociation of Schiff base bonds. As a result, it demonstrates strong antibacterial activity against both Gram-positive bacteria S. aureus and Gram-negative bacteria E. coli through contact killing and diffusion killing mechanisms. Importantly, the OHA-PBA/PVA/Gen hydrogel avoids incorporation of toxic small molecular crosslinking agents, and all the components of the hydrogel are biocompatible, ensuring its biosafety. In a S. aureus-infected wound mouse model, this hydrogel effectively eradicated bacteria and promoted angiogenesis, leading to significantly accelerated wound healing. These results highlight the potential of the dual dynamically crosslinking hydrogel OHA-PBA/PVA/Gen as a multifunctional wound dressing for the treatment of bacteria-infected wound.

An Environmentally Stable, Biocompatible, and Multilayered Wound Dressing Film with Reversible and Strong Adhesion.

Reversible adhesives for wound care improve patient experiences by permitting reuse and minimizing further tissue injury. Existing reversible bandages are vulnerable to water and can undergo unwanted deformation during removal and readdressing procedures. Here, a biocompatible, multilayered, reversible wound dressing film that conforms to skin and is waterproof is designed. The inner layer is capable of instant adhesion to various substrates upon activation of the dynamic boronic ester bonds by water; intermediate hydrogel layer and outer silicone backing layer can enhance the dressing's elasticity and load distribution for adhesion, and the silicone outer layer protects the dressing from exposure to water. The adhesive layer is found to be biocompatible with mouse skin. Skin injuries on the mouse skin heal more rapidly with the film compared to no dressing controls. Evaluations of the film on skin of freshly euthanized minipigs corroborate the findings in the mouse model. The film remains attached to skins without delamination despite subjecting to various degrees of deformation. Exposure to water softens the film to allow removal from the skin without pulling any hair off. The multilayered design considers soft mechanics in each layer and will offer new insights to improve wound dressing performance and patient comfort.

Building covalent crosslinks of carboxymethyl konjac glucomannan with boronic ester bonds for fabricating multimodal hydrogel sensor

As the derivative of konjac glucomannan (KGM), carboxymethyl konjac glucomannan (CMK) has attracted increasing attention in the polysaccharide hydrogel fields with the aim of improving the performance related to drug delivery and release. In this study, we prepared a CMK-based hydrogel with dual characteristic crosslinks, and unlocked new applications of this type of hydrogel in soft sensor fields. CMK and poly (vinyl alcohol) were used as substrates, and physical crosslinks were constructed via the freeze-thawing treatments and covalent crosslinks were built via the boronic ester bonding. As-prepared hydrogel possessed significantly improved mechanical performance because the boronic ester bonding, on the one hand, well associated the two kinds of polymer chains, and on the other hand, played the role of ‘sacrificial crosslinks’. Furthermore, the occurrence of dynamic boronic ester bonding gave the hydrogel strain- and temperature-sensitive ionic conductivity, and therefore, the hydrogels could be used to identify human motions and as-resulted environmental temperature alterations, and worked well in various scenarios. This work activates new application of CMK in the multimodal sensing field, and also proposes an intriguing way of building multiple crosslinks in the KGM derivative-based hydrogels.

Dynamic Covalent Bonds Enabled Carbon Fiber Reinforced Polymers Recyclability and Material Circularity

AbstractDue to their remarkable features of lightweight, high strength, stiffness, high‐temperature resistance, and corrosion resistance, carbon fiber reinforced polymers (CFRPs) are extensively used in sports equipment, vehicles, aircraft, windmill blades, and other sectors. The urging need to develop a resource‐saving and environmentally responsible society requires the recycling of CFRPs. Traditional CFRPs, on the other hand, are difficult to recycle due to the permanent covalent crosslinking of polymer matrices. The combination of covalent adaptable networks (CANs) with carbon fibers (CFs) marks a new development path for closed‐loop recyclable CFRPs and polymer resins. In this review, we summarize the most recent developments of closed‐loop recyclable CFRPs from the unique paradigm of dynamic crosslinking polymers, CANs. These sophisticated materials with diverse functions, oriented towards CFs recycling and resin sustainability, are further categorized into several active domains of dynamic covalent bonds, including ester bonds, imine bonds, disulfide bonds, boronic ester bonds, and acetal linkages, etc. Finally, the possible strategies for the future design of recyclable CFPRs by combining dynamic covalent chemistry innovation with materials interface science are proposed.

Multi-responsive sodium hyaluronate/tannic acid hydrogels with ROS scavenging ability promote the healing of diabetic wounds

Oxidative stress caused by excessive reactive oxygen species (ROS) accumulation significantly hinders wound healing in patients with diabetes. Scavenging ROS and reducing inflammation are crucial for rapid healing. In this work, a multi-responsive sodium hyaluronate (HA)/tannic acid (TA) hydrogel was developed based on boronate ester bonds. Sodium hyaluronate with 3-aminophenyl boronic acid modification (HA-APBA) was mixed and crosslinked with TA to form HA-APBA/TA hydrogels. These hydrogels are injectable, self-healing, and biocompatible. The HA-APBA/TA hydrogels could release free TA through the collapse of the structure at low pH, high H2O2 concentration, and high glucose concentration, thus possessing good ROS scavenging ability. In full-thickness skin wounds of db/db mice, the HA-APBA/TA hydrogels promoted wound healing, collagen deposition, and significant angiogenesis. Furthermore, they have been shown to effectively reduce the levels of inflammatory factors in wounds and lower the expression of CD86, a pro-inflammatory macrophage surface marker. This resulted in a more effective transition of wound healing from the inflammatory phase to the proliferative phase. This study provides an optional strategy for alleviating oxidative stress and controlling excessive inflammation, thereby promoting diabetic wound healing.

Lignin-based vitrimer containing dynamic borate ester bonds with intrinsic photoconversion and excellent photothermal remoldability

The development of photoresponsive shape memory materials based on the photothermal conversion properties of lignin and the low activation energy of the dynamic covalent borate bond is of great importance. In this paper, a kind of lignin-based vitrimer polymer (LBP) containing dynamic boronic ester bonds was prepared by a “sulfhydryl-epoxy” click reaction and etherification reaction. The results show that the rigid segment EP-EL (lignin-based epoxy resin) and BDB (2,2′-(1,4-phenylene)-bis-[4-mercapto-1,3,2-dioxaneborane]) with benzene ring structure can impart tensile strength (20.8 MPa) to the LBP, while the flexible segment PEG imparts good elongation at break (15 %). The dynamic binding and dissociation exchange mechanism of the boronic ester bonds enables LBP to exhibit thermal remodelling properties (up to 36.2 %) and water-assisted self-healing properties at room temperature (up to 49.0 %). In addition, LBP exhibits excellent thermal and light-responsive shape memory properties due to its own photothermal conversion performance (photothermal conversion efficiency up to 18.2 %) and the dynamic boronic ester bond thermal activation bond exchange mechanism. The insulating properties of LBP make it suitable for use in high temperature protection circuit devices and light-responsive circuit devices. This study provides new insights into the design and application of Vitrimer and photoresponsive shape memory polymers, and also offers a new avenue for high-value utilization of lignin.

Hyaluronic Acid-Based Microparticles with Lubrication and Anti-Inflammation for Alleviating Temporomandibular Joint Osteoarthritis.

The pathogenesis of temporomandibular joint osteoarthritis (TMJOA) is closely associated with mechanical friction, which leads to the up-regulation of inflammatory mediators and the degradation of articular cartilage. Injectable drug-loaded microparticles have attracted widespread interest in intra-articular treatment of TMJOA by providing lubrication and facilitating localized drug delivery. Herein, a hyaluronic acid-based microparticle is developed with excellent lubrication properties, drug loading capacity, antioxidant activity, and anti-inflammatory effect for the treatment of TMJOA. The microparticles are facilely prepared by the self-assembly of 3-aminophenylboronic acid-modified hyaluronic acid (HP) through hydrophobic interaction in an aqueous solution, which can further encapsulate diol-containing drugs through dynamic boronate ester bonds. The resulting microparticles demonstrate excellent injectability, lubrication properties, radical scavenging efficiency, and antibacterial activity. Additionally, the drug-loaded microparticles exhibit a favorable cytoprotective effect on chondrocyte cells invitro under an oxidative stress microenvironment. Invivo experiments validate that intra-articular injection of drug-loaded microparticles effectively alleviates osteoporosis-like damage, suppresses inflammatory response, and facilitates matrix regeneration in the treatment of TMJOA. The HP microparticles demonstrate excellent injectability and encapsulation capacity for diol-containing drugs, highlighting its potential as a versatile drug delivery vehicle in the intra-articular treatment of TMJOA.

Photocurable vitrimers with malleable and self-healing trade-off enabled by manipulating dynamic boronic ester bonds

Although numerous strategies refer to dynamic covalent bond exchanges of small molecules for self-repairing thermosets, it remains a critical challenge to be able to jointly tune the malleability and dynamic properties of photocurable materials via extending dynamical small molecule bridging chains with tunable kinetic features. Herein, we successfully synthesized two typical diboronic ester molecules (diboronic ester dithiol/diacid) with variable dioxaborolane metathesis kinetics, which acted as dynamical interlinking segments constructing simple hydrogenated bisphenol A (HBA) epoxy backbone to achieve dynamically cross-linking feature. Subsequently, the acrylate- and anhydride-modified HBA vitrimers bearing diboronic ester-extending segment variants and photocuring traits are successfully synthesized by a one-pot reaction. Consequently, it is demonstrated that the embedded amounts of dynamic diboronic ester bonds in the backbone play a key role in the photopolymerization rate of photocurable vitrimers. The photopolymerization rate decreases significantly as more diboronic ester segments. Moreover, the diboronic ester dithiol-mediated photocurable vitrimer (HBA-S) exhibits enhanced malleability (strain at break of 26.6 %), desirable photo-crosslinked network, and accelerated thermal-triggered self-healing ability (scratch self-healing efficiency of closing to 100 % at 150 °C), compared to those of the diboronic ester diacid-mediated vitrimer (HBA-O) under identical conditions. This work validates the probability of transferring the dioxaborolane metathesis of small molecules to dynamic properties of bulk UV-curing materials, which provides valuable guidance for the rational design and fabrication of tunable dynamic photocurable materials.