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ACS Applied Materials & Interfaces · 2025 · IF 8.2

Wood-Inspired Dynamic Covalent Cross-Linking Network for Ultrahigh Adhesion Strength, Desired Weather Resistance, and Closed-Loop Recycling Adhesives

Xuebin Lian,Yuanjian Li,Penghui Li,Yilin Jin,Xinyu Zhao,Jiangwen Li,Dehuan Kong,Shujun Zhao,Shuangfei Xiang,Feiya Fu,Xiangdong Liu

The problems of strength–toughness trade-off and stability–switchability conflict make it a huge challenge to integrate exceptional adhesion and desired recycling performances into a single system. Inspired by wood cellulose molecular chain structure, a parallel-ordered dynamic boronic esters cross-linking network is presented by using 4-dimethylaminopyridine as a countercation stabilizing the boron center to induce boric acid to form ionic spiroborate linkage with linear hydroxyl-decorated epoxy polymer. The ionic spiroborate polymer network has a high cross-linking degree to contribute to structural stability and adhesion strength. Moreover, the unique ionic spiroborate bond cooperates with the parallel-ordered structure, providing a highly effective path and a rapid exchange rate and thus affording excellent closed-loop recycling properties. Given the effects, a superior adhesion strength of 30.86 ± 0.74 MPa is found along with an excellent debonding work of 64929 N m–1. Also, adhesives show excellent environmental reliability. In addition, the prepared adhesives exhibit good chemical/physical recyclability and display 106.8% conservation of adhesion strength after 3 bonding and debonding tests. This work provides a strategy to construct high-performance adhesives that combine robust adhesion and recyclable properties.

研究领域: 材料科学 · 高分子化学 · 胶粘剂技术 · 可持续化学
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EUROPEAN POLYMER JOURNAL · 2024 · IF 5.8

Shifting the mechanical strength-healing efficiency trade-off of polyurethanes by incorporating boronic ester bonds and hydrogen bonding

Sikun Fang,Wanting Zeng,Long Liu,Yuan Lyu,Fuwei Dong,Lin Wan,Yingjun Liu,Aihua Du

It is challenging to design and synthesize elastomers with both good mechanical performance and high healing efficiency because their mechanisms are mutually exclusive. This work aims to shift the trade-off between them by incorporating dynamic non-covalent bonds via 2-ureido-4[1H]-pyrimidione (UP y ) and dynamic covalent bonds via boronic ester bonds into polyurethane. The quadruple hydrogen bonds between UP y dimers serve as physical crosslinks, improving the overall mechanical properties of the polyurethane, while the boronic esters facilitate its healing. The resulting polyurethane can achieve an ultimate stress of 27.4 MPa and a healing efficiency of 90 %. The effect of healing time on the healing efficiency is modeled and discussed.

CAS / MDL: 25190-06-1
研究领域: 材料科学 · 化学
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Chemical Science · 2025 · IF 7.4

Electric-Field-Induced Covalent Condensation of Boronic Acids in Water Microdroplets

Yue-Wen Zhou,Ming-Yang Jia,Jun-Lei Yang,Qinlei Liu,Zhenfeng Cai

The influence of electric fields (EFs) on chemical reactions has attracted significant interest due to their ability to modulate reaction rates, pathways, and selectivity. Although EFs have been experimentally demonstrated to facilitate various reactions, clearer evidence for their role in covalent condensation has remained limited. Herein, we provide experimental evidence of electric-field-induced covalent condensation of boronic acids, utilizing the strong EFs at the air-liquid interface of microdroplets to induce the reaction. Microdroplet-based chemistry provides interfacial electric field intensities as high as ca. 109 V/m, offering a robust platform for the systematic investigation of boronate linkage formation and subsequent condensation of boronic acids. Our results confirm the role of EFs in facilitating room-temperature condensation of boronic acids, providing direct insights into the electric-field-induced polymerization process and presenting an experimental approach for investigating these processes in solution.

CAS / MDL: 4151-80-8 4612-26-4
研究领域: 化学 · 材料科学
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COMPOSITES PART A-APPLIED SCIENCE AND MANUFACTURING · 2024 · IF 8.1

Self-healing thermally conductive polymer composites based on polyvinyl alcohol with dynamic borate ester and hydrogen bonds

Xing Xie,Dan Yang

Traditional thermally conductive polymer materials exhibit a propensity for damage when applied in dynamic environments, which leads to shortened service life and suboptimal utilization of resources. Herein, polyvinyl alcohol (PVA)-based thermally conductive composites with a self-healing capability are prepared based on dynamic borate ester bonds and hydrogen bonds. Poly(dopamine) functionalized graphene oxide (denoted as PGO) is used as a thermally conductive filler to achieve a high thermal conductivity (TC) of 0.79 W/(m·K) for the PGO/PVA composites, which is 527% of pure PVA (0.15 W/(m·K)). The improved TC of PGO/PVA composites is mainly attributed to the reduction in interface thermal resistance and the construction of heat conduction channels. Additionally, the PGO/PVA composites display a self-healing efficiency higher than 60% at room temperature without external simulation. Furthermore, the as-prepared PGO/PVA composites exhibit excellent mechanical properties, with a tensile strength of 409 kPa and an elongation at break of 479%, respectively. This work provides a promising strategy for fabricating thermally conductive polymer composites, which can be deployed as thermal interface materials for long-term applications.

CAS / MDL: 107-22-2
研究领域: 材料科学 · 高分子化学
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POLYMER · 2021 · IF 4.43

Phosphate enhanced self-healing property of phenylborate-based hydrogel at neutral environment

Yongjie Dong,Siqi Chen,Piao Ning,Ka Lu,Song Ma,Yingjie Wang,Shaoyu Lü

Self-healing hydrogels based on phenylboronate ester bonds are of huge interest in polymer science. However, most of these hydrogels only heal themselves at pH above their pKa (mostly > 8.0), which reduces their potential application in physiologic environments. Here, we showed that a small amount of phosphate produced stable hydrogels, able to support their self-healing at neutral pH. The hydrogel was formed by poly (3-acryloxymethylphenylboronic acid- co -N, N-dimethyl acrylamide) and poly (D-gluconamidoethyl methacrylate- co -N, N-dimethyl acrylamide) in phosphate buffer. Self-healing was observed at pH = 7.0. Intermolecular interactions between phenylboronic acid and phosphate were suggested by rheology, DSC determination and QTAIM calculations. The study represents a new mechanism to promote phenylboronate-based hydrogel formation and self-healing at neutral environment and, more importantly, provides considerable insight into their application in physiologic conditions including sensors and tissue engineering.

研究领域: 材料科学 · 生物医学工程
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JOURNAL OF POLYMER SCIENCE · 2025 · IF 3.6

pH and ROS Dual-Responsive Core-Cross-Linked Micelles Based on Boronic Ester Linkage for Efficient PTX Delivery

Sunqi Yu,Siyuan Chen,Tianrui Tong,Yunfeng Yan,Qi Shuai

Micelle-based drug delivery systems (DDS) have emerged as a promising solution to address challenges associated with the in vivo delivery of hydrophobic anticancer chemotherapeutics. However, micelles still encounter issues such as drug pre-leakage and poor stability in physiological conditions. To overcome these limitations, we developed a core-cross-linking strategy utilizing amphiphilic copolymers, mPEG- b- P(AVL- co -LA) (mPPAL), functionalized with phenylboronic acid (PBA), and catechol by CuAAc “click” chemistry, respectively. These copolymers self-assembled into core-cross-linked micelles (CLMs), featuring boronic ester bonds, which were characterized through a series of evaluations. The CLMs exhibited a rational particle size, uniform morphology, low critical micelle concentration (CMC), high PTX loading capacity, and excellent stability. Two promising micelles, CLM1 and CLM3, were identified, and their responsiveness to acidic pH and elevated levels of ROS was confirmed to enable controlled PTX release. The results of MTT assay and hemolytic analysis demonstrated high biocompatibility and potential in vivo application of these selected CLMs. The anticancer efficacy of the selected PTX-CLMs was further validated through MTT assay and 3D tumor spheroid studies. Fluorescence microscopy and flow cytometry demonstrated rapid intracellular uptake of the CLMs. In vivo biodistribution studies demonstrated successful accumulation in the targeted tumor tissue. These findings suggest that the boronic ester-based CLMs developed in this study are a promising nanocarrier for effective PTX delivery. Graphical Phenylboronic acid (PBA) and catechol-modified amphiphilic copolymers (mPPAL@R) were synthesized via ring-opening polymerization followed by CuAAc click chemistry. These copolymers were employed to construct pH- and ROS-dual-responsive micelles with boronic ester core-crosslinking. A series of in vitro and in vivo experiments were conducted to evaluate PTX-loaded micelles, demonstrating their significant potential for effective PTX delivery.

CAS / MDL: 7385-67-3
研究领域: 药剂学 · 肿瘤学 · 材料科学
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EUROPEAN POLYMER JOURNAL · 2024 · IF 5.8

Dual network hydrogel sensors based on borate ester bond: Multifunctional performance in high conductivity, stretchability, mechanical strength, and anti-freezing properties

Chunjiao Liu,Haoran Wu,Ruixue Wang,Yajuan Li,Xudong Yu

Conductive polymer hydrogels have attracted great attention due to their application prospects in the fields of health care monitoring, wearable electronics and soft robots. Developing hydrogel sensors with robust mechanical characteristics, outstanding sensing abilities, the ability to self-heal and adhere effectively is critical, yet it remains a major challenge. Here, we present a simple one-pot method to prepare a dual-network flexible hydrogel based on polyvinyl alcohol (PVA), acrylamide (AM), pyridine-4-boronic acid derivatives (PBAD), and lithium chloride (LiCl). The cross-linked network is established through reversible and dynamic borate ester bonds, hydrogen bonds, electrostatic interactions and coordination bonds, imparting outstanding mechanical and self-healing characteristics to the material. The incorporation of PBAD not only imparts high conductivity (9.84 mS·cm −1 ) and sensitive sensing performance (GF = 13.89) to the hydrogel, but also synergistically improves its elongation (1689 %), tensile strength (0.6 MPa), and toughness (5.74 MJ/m 3 ). In addition, based on the participation of LiCl, the hydrogel shows outstanding anti-freezing properties. This work is expected to provide new ideas for the assembly of high performance flexible sensor and to expand their application in electronic skin, wearable devices, and soft actuators.

CAS / MDL: 9002-89-5
研究领域: 材料科学 · 生物医学工程
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Fluorescence-color-changing biomimetic tough films with simultaneous shape-deformation triggered by pH

Junyi Tang,Yuanyuan Ren,Jiachun Feng

Stimuli-responsive materials with complex practical functions that could imitate certain behaviors of living organisms have wide potential applications in frontier fields. However, the fabrication of stimuli-responsive films with simultaneous change in fluorescence color and shape in response to a single stimulus, especially by a simple fabrication strategy, remains a challenge. Herein, a simple hydrogel-film-post crosslinking strategy is proposed to prepare films that exhibit fluorescence change accompanying with shape deformation under pH stimulus. The synchronous changes are realized by the combination of dynamic boron chemistry and pH-sensitive lanthanide complexes. Under different pH conditions, the protonation/deprotonation of the ligands coordinated to Eu 3+ ions could generate switchable on/off fluorescence behavior, while the association/dissociation of borate ester bonds between 3-aminobenzeneboronic acid (SA-PBA) and polyvinyl alcohol (PVA) could lead to macroscopic deformation. The existence of borate ester bonds is beneficial to the mechanical properties of composite films. Under pH stimulus, the film-based artificial flower could simulate the flowering of natural flowers accompanying with color changes and the film-based gripper could grasp object with a visual signal, which demonstrates that the SA-PBA/PVA/EuL films have great potential for wide application.

研究领域: 材料科学 · 仿生学
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COLLOIDS AND SURFACES B-BIOINTERFACES · 2016 · IF 3.902

Nanomicelles based on a boronate ester-linked diblock copolymer as the carrier of doxorubicin with enhanced cellular uptake

Yan Xu,Yuanyuan Lu,Lei Wang,Wei Lu,Jin Huang,Ben Muir,Jiahui Yu

This study sought to develop a new type nanomicelle based on boronate ester-linked poly(ethylene glycol)- b -poly(benzyl glutamate) (PEG-BC-PBLG) diblock copolymer as the carrier of doxorubicin (Dox) to achieve acid-induced detachment of PEG shells and subsequent boronic acid-mediated enhanced endocytosis. In vitro studies revealed that the PEG-BC-PBLG copolymer was stable in neutral solutions but tend to hydrolysed under acidic conditions, which was attributed to the acid-sensitive properties of boronate ester bonds. The formation of PEG-BC@PBLG micelles was confirmed based on critical micelle concentration (CMC), particle size, and morphology observations. It was observed that these micelles were spherical with an average particle size of approximately 80   nm, as measured by dynamic laser scattering (DLS), suggesting their passive targeting to tumour tissue and endocytosis potential. Dox-loaded PEG-BC@PBLG micelles (PEG-BC@PBLG·Dox) showed sustained drug release profiles over 9   h, and their cumulative drug release was dependent on the pH value of the environment. Remarkably, cellular uptake ability of PEG-BC@PBLG micelles was found to be higher than that of non-boronate ester-linked PEG@PBLG micelles due to boronic acid-mediated endocytosis, as revealed by confocal laser scanning microscopy (CLSM) imaging of fluorescein isothiocyanate (FITC) green-conjugated micelles, thereby providing higher cytotoxicity against HepG2 cells. The antitumour activity and toxicity of PEG-BC@PBLG·Dox micelles in vivo were evaluated in BLAB/c mice against HepG2 cell-derived tumours. Compared with Dox, PEG-BC@PBLG·Dox showed reduced toxicity, whereas its tumour growth inhibition rate was 17% higher than that of free Dox. These results indicate the great potential of PEG-BC@PBLG micelles as the carrier of various lipophilic anticancer drugs with improved anti-tumour efficacy.

研究领域: 药剂学 · 肿瘤学 · 生物材料学
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Science Advances · 2025 ·Vol. 11 ·期 4 · IF 12.5

Salt-welding strategy for the design of repairable impact-resistant and wear-resistant hydrogels

Jiangpeng Jia,Shan Lu,Shurui Sun,Yijie Jin,Liguo Qin,Chuanzhuang Zhao

Self-healing hydrogels can autonomously repair damage, enhancing their performance stability and broadening their applications as soft devices. Although the incorporation of dynamic interactions enhances self-healing capabilities, it simultaneously weakens the hydrogels’ strength. External stimuli such as heating, while accelerating the healing process, may also lead to dehydration. Developing a stable repair strategy that combines rapid healing and high mechanical strength is challenging. Here, we introduce “salt-welding” for high-strength hydrogels with rapid room temperature self-healing. This is achieved through dynamic borate ester bonds in a salt-responsive poly(methacrylamide) hydrogel. The process involves “salt-fusion” to convert fractures into a viscous liquid for swift healing, followed by “salt-concretion” to toughen the hydrogel. The hydrogels achieve a posthealing strength of 23 megapascals in 95 minutes at room temperature, with near 100% healing efficiency. Leveraging their tunable mechanical strength and rapid healing rate, the hydrogel can be tailored for applications as a reparable wear-resistant material and damping device.

研究领域: 材料科学 · 生物医学工程
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ACS Applied Polymer Materials · 2025 · IF 4.7

Self-Healing Waterborne Polyurethane Coatings Based on Dynamic Covalent Borate Esters with Boron–Nitrogen Internal Coordination

Xing Zhang,Jiangling Bai,Rui Xu,Jinda Peng,Qian Han,Lei He,Yuanyuan Ma,Guowei Da,Juqing Cui

Waterborne polyurethane (WPU) coatings frequently experienced surface and interior damage during long-term use, leading to small cracks and significantly diminishing their protective and aesthetic properties, thereby reducing their service life. To address these challenges, we synthesized a borate ester-bonded compound with boron–nitrogen internal coordination (MN). Subsequently, a self-healing WPU coating was successfully prepared using polytetrahydrofuran (PTMEG-1000), diphenylmethane diisocyanate (MDI), a hydrophilic chain extender of 2,2-bis(hydroxymethyl)propionic acid (DMPA), and a borate-ester chain extender of MN. The results indicated that the storage stability of WPU emulsions containing MN was enhanced, maintaining stability without stratification for up to 30 days and remaining stable after centrifugation. The incorporation of MN into WPU films conferred an 83% self-healing ability, a tensile strength of 24.2 MPa, and significantly improved thermal stability. Additionally, WPU paint films containing MN exhibited superior water resistance, with no visible degradation after 24 h of immersion and a water absorption rate of only 10.0%. Moreover, the mechanical properties of WPU paint films with MN were also enhanced, demonstrating a hardness of 5H, an adhesion grade of 0, an impact resistance exceeding 50 cm, and a flexibility of 1 mm. At the same time, WPU paint films containing MN exhibited self-healing capabilities, effectively repairing cross-scratches. This study provided an approach for the development of WPU coatings technology, which demonstrated that self-healing WPU has potential applications in aerospace coatings, the automotive industry, and household products.

CAS / MDL: 59016-93-2
研究领域: 材料科学 · 化学工程
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CHINESE JOURNAL OF POLYMER SCIENCE · 2025 · IF 4

Monitoring the Interfacial Polymerization and Membrane Fouling of Selective Layer with Boronate Ester Linkages via Aggregation-induced Emission

Zhao Meng-Yao,Luo Xin-Zhao,Li Die,Dong Ya-Qi,Wang Qian,Xu Xiao-Ling,Zhang Qiang

It is important to understand the evolution of the matter on the polymer membrane surface. The in situ and real-time monitoring of the membrane surface will not only favor the investigation of selective layer formation but can also track the fouling process during operation. Herein, an aggregation-induced emission (AIE)-active polymer membrane was prepared by the interfacial polymerization of a cyclodextrin-based glycocluster (CD@Glucose) and a tetraphenylethylene derivative modified with boronic acid groups (TPEDB) on the surface of a polyacrylonitrile (PAN) ultrafiltration membrane. This interfacial polymerization method can be stacked layer-by-layer to regulate the hydrophilicity and pore structure of the membrane. With the increase in the number of polymer layers, the separation and antifouling properties of the membrane gradually improved. Owing to the AIE property of the crosslinking agent TPEDB, the occurrence of interfacial polymerization and the degree of fouling during membrane operation can be monitored by the fluorescence distribution and intensity. With the aggravation of membrane fouling, the fluorescence decreased gradually, but recovered after cleaning. Therefore, this AIE effect can be used for real-time monitoring of interfacial polymerization as well as membrane fouling.

CAS / MDL: 9048-46-8
研究领域: 高分子化学 · 膜科学 · 材料表征 · 荧光监测
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