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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Dual dynamic network structures of recyclable epoxy resins with high strength and toughness via sacrificial hydrogen-bonding clusters and imine bonds: surpassing the strength-toughness trade-off

Cheng-wang Shi,Xiao-dong Li,Xu-feng Zhang,Mei-shuai Zou

Thermosetting epoxy resins with high strength , high toughness, and recyclability are strongly sought after, but due to crosslinked structure, balancing strength and toughness and achieving degradation and reprocessing of resins is a challenge. Enhancing strength without compromising toughness during designing recyclable epoxy resin is a challenging task. Herein, a solution is demonstrated where isofluorodioxanone diisocyanate (IPDI), Poly (propylene glycol) bis(2-aminopropyl ether) (D230), and naturally occurring vanillin synthesized a novel imine-functionalized epoxy monomer (IDV-EP), and cured with diamino-diphenylmethane (DDM), 2-(4-aminophenyl)-1H-benzimidazol-5-amine (APBIA) and 4, 4-diamino benzoyl triphenylamine (DABA), respectively, for the purpose of building different contents of the sacrificial hydrogen-bonding clusters (SHBC) in topological network structures. As the hydrogen-bonding (H-bonding) binding energy of the crosslinked network increases, the strength and toughness of the resin were increased concurrently, SHBC was demonstrated to be a feasible method to achieve the strength-toughness trade-off of thermosets, in which IDV-EP-DABA illustrated a tensile strength of 90 MPa, an elongation at break of 16.5%, as well as toughness of 9.73 MJ/m 3 , which was higher than that of the ordinary bisphenol A-type epoxy thermosetting resin (DGEBA/DDM) by 1.8, 3.7 as well as 6.7 times, respectively. Furthermore, the covalent adaptive networks (CANs) formed by imine bonds provide the resins with effective capabilities for swift degradation (rapid degradation in acid/solvent, room temperature and static conditions) and reprocessing (only a slight decrease in the mechanical properties after hot pressed at 180°C/10 MPa for 15 minutes) , showcasing promising prospects for sustainable utilization.

研究领域: 材料科学 · 化学工程
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Polymers · 2018 ·Vol. 10 ·期 10 ·1127 · IF 2.935

Design, Synthesis, and Characterization of Schiff Base Bond-Linked pH-Responsive Doxorubicin Prodrug Based on Functionalized mPEG-PCL for Targeted Cancer Therapy

Yinglei Zhai,Xing Zhou,Zhiqiang Zhang,Lei Zhang,Dianyu Wang,Xinhui Wang,Wei Sun

The side effects of doxorubicin (DOX) extremely limit its application in the treatment of malignant tumors. Nano-sized polymeric drugs based on the acidic microenvironment of tissular- or intra- tumor have attracted ample attention because of their potential in reducing side effects. In this research, an amphiphilic diblock copolymer based on poly (ethylene glycol) (PEG) and functionalized polycaprolactone (PCL) was synthesized and utilized as the drug carrier. DOX was chemically conjugated with the polymer via acid-cleavable imine bonds to obtain a novel pH-sensitive DOX prodrug (mPEG-PCL-Imi-DOX). mPEG-PCL-Imi-DOX (24.2 wt % DOX content) formed micelles with an average diameter of 125 nm through a simple solvent evaporation method. The in vitro release profile demonstrated that DOX release of the prodrug micelles was pH-responsive and able to be accelerated with the decrease of pH. In vitro cytotoxicity assay tests revealed that the pH-sensitive DOX prodrug micelles exhibited relatively lower toxicity and similar antitumor efficacy towards MCF-7 cells compared with free DOX. Hence, the DOX prodrug micelles with imine bonds can offer a carrier with great potential for chemo-therapeutics.Keywords:doxorubicin;pH-sensitive;prodrug;micelles;imine

研究领域: 药学 · 肿瘤学
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Soft Matter · 2019 ·Vol. 15 ·期 47 ·9797-9804 · IF 3.399

Dual-cross-linked dynamic hydrogels with cucurbit[8]uril and imine linkages

Jin Zhang,Shengzhen Hou,Yanru Chen,Jing Zhou,Hao Chen,Yebang Tan

The strategy of dual cross-linking was investigated by enhancing the performance of dynamic hydrogels. To this end, phenylalanine modified ε-polylysine was synthesized and employed as the polymer backbone of hydrogels. The phenylalanine moieties and amine groups of the polymer could be cross-linked with cucurbit[8]uril (CB[8]) and the dialdehyde cross-linker, respectively. Single CB[8] linkage with fast dynamics led to an increase in the viscosity of the polymer solution, and single imine linkage with slow dynamics led to the formation of weak and brittle hydrogels. However, the two linkages were combined together to form a dual-cross-linked hydrogel and the performance of the hydrogel could be well enhanced. Compared with the single imine cross-linked hydrogel, the dual-cross-linked hydrogel demonstrated a higher mechanical strength, better extensibility and faster self-healing rate. It is anticipated that this line of research could provide a useful method to enhance the performance of dynamic hydrogels.

CAS / MDL: 3674-06-4 25322-68-3
研究领域: 材料科学 · 生物化学
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BIOMACROMOLECULES · 2017 · IF 5.246

Enzyme-Regulated Fast Self-Healing of a Pillararene-Based Hydrogel

Xin Zhang,Jiayun Xu,Chao Lang,Shanpeng Qiao,Guo An,Xiaotong Fan,Linlu Zhao,Chunxi Hou,Junqiu Liu

Self-healing, one of the exciting properties of materials, is frequently used to repair the damage of biological and artificial systems. Here we have used enzymatic catalysis approaches to develop a fast self-healing hydrogel, which has been constructed by dynamic aldimine cross-linking of pillar[5]arene-derivant and dialdehyde-functionalized PEG followed by encapsulation of glucose oxidase (GOx) and catalase (CAT). In specific, the two hydroxyl groups at terminal of PEG4000 are functionalized with benzaldehydes that can interact with amino-containing pillar[5]arene-derivant through dynamic aldimine cross-links, resulting in reversible dynamic hydrogels. Modulus analysis indicated that storage modulus (G′) and loss modulus (G″) of the hydrogel increased obviously as the concentration of dialdehyde-functionalized PEG4000 (DF-PEG4000) increased or the pH values decreased. Once glucose oxidase (GOx) and catalase (CAT) are located, the hydrogel could be fast repaired, with self-healing efficiency up to 100%. Notably tensile test showed that the repair process of pillararene-based hydrogel can finish in several minutes upon enzyme catalysis, while it needed more than 24 h to achieve this recovery without enzymes. This enzyme-regulated self-healing hydrogel would hold promise for delivering drugs and for soft tissue regeneration in the future.

研究领域: 材料科学 · 生物医学工程
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2024 · IF 4.9

Polyurethane combining preeminent toughness, puncture-resistance, and self-healing capabilities by multiple repair options based on dual dynamic covalent bonds

Jiaofeng Ye,Junxiang Zhang,Libang Feng,Haocheng Liu,Danbin Zhu,Yanhua Liu

The development of self-healing materials has enabled the production of more reliable and intelligent materials. However, resolving the conflict between mechanical strength and self-healing efficiency as well as limited repair options of the self-healing materials is still the most pressing scientific challenge. In this study, a self-healing polyurethane with multiple repair methods is prepared by introducing disulfide bonds into thermo-reversible imine bonds-based polyurethane . The resultant polyurethane exhibits impressive comprehensive mechanical properties and preeminent repair capabilities. More importantly, damages can be repaired through various routes such as room temperature, moderate temperature, hair dryer blowing, and ethylenediamine assistance treatments. The superior mechanical properties, repetitive self-healing performance, and multiple options for repair is attributed to the cooperation of thermally reversible imine and disulfide exchanges, thermal motion of molecular chains , and dissociation/regeneration of hydrogen bonds . So this research provides numerous ideal options for repairing cracks and other damages in materials used in construction industry under different usage environments. Consequently, high-quality repairs, improved efficiency, and extended service life of construction engineering materials can be ensured.

研究领域: 材料科学 · 化学工程
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2015 · IF 2.752

pH-responsive vesicles from supra-amphiphiles based on dynamic imine bond

Jiao Wang,Xiao Chen,Wanling Cui,Sijing Yi

pH-responsive vesicles have been prepared from the mixture of 1-(10-(4-formyl-phenoxy) decyl)-pyridinium (FDP) or 1-methyl-3-(10-(4-formyl-phenoxy) decyl) imidazolium (FDI) with 1-octyl amine at a molar ratio of 1:1 in alkaline aqueous solutions. Their structures and morphologies were characterized by transmission electron microscopy with sample preparations by negative staining or freeze-fracture. Basically, the spherical unilamellar vesicles were formed with the mean diameters respectively of about 71 and 107   nm for two supra-amphiphile systems, which were based on the formation of dynamic imine bonds between amine and FDP (i-FDP) or FDI (i-FDI). The loading and release studies of a fluorophore, Nile red (NR), demonstrated the capabilities of these vesicles to encapsulate NR and a rapid release at low pH environment. The vesicles from i-FDP behaved relatively more sensitive to acidic environment than those from i-FDI. The dynamic transitions of supra-amphiphiles were characterized by nuclear magnetic resonance or fluorescence emission spectroscopy measurements. A lower critical micelle concentration and a higher aldehyde conversion efficiency of i-FDI than those of i-FDP were observed. The characteristics of facile formation, fast dissociation, and switchable morphologies of studied systems should be referable for designing novel smart supra-amphiphile systems with potential applications as controlled drug delivery systems.

研究领域: 生物化学 · 材料科学 · 药物递送
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ACS Applied Polymer Materials · 2025 · IF 4.7

Biphenyl-Based High Thermal Conductivity Films with Intrinsic Self-Healing Properties

Yanhan Tao,Hui Yang,Zhijun Liu,Guoming Yuan,Kunxin Wang,Kun Wu,Jun Shi

One kind of liquid crystal monomer (LM) based on a biphenyl mesomorphic unit was synthesized from 4,4′-biphenyldicarboxaldehyde and 4-amino-3-methylphenol. Then two films (LM/TPTMP and LM/PETMP) were prepared by reacting the two thiols (TPTMP and PETMP) with the liquid crystal monomer (LM), respectively. These two films simultaneously exhibit intrinsically high thermal conductivity and intrinsic self-healing properties. Due to the presence of biphenyl liquid crystal units in LM and its highly symmetrical structure, a distinct nematic liquid crystal phase can be observed through a polarized optical microscope when heated to the liquid crystal phase transition temperature. The crystallite size of LM was calculated as 37 nm by an X-ray diffractometer (XRD). The films exhibit outstanding thermal conductivity, with LM/TPTMP achieving a thermal conductivity in the horizontal direction (λ∥) of 0.700 W/(m·K), which is significantly higher than that of epoxy resin-based intrinsic thermal conductivity materials in the range of 0.2–0.4 W/(m·K). The introduction of thiol flexible segments endowed the materials with good mechanical strength, with LM/PETMP demonstrating a tensile strength of 4.74 MPa and an elongation at break of 42.57%. Furthermore, the incorporation of dynamic imine bonds imparted excellent self-healing properties to the films. Specifically, LM/PETMP could retain 73% and 65.2% of its original tensile strength after one and three cycles of self-healing behavior, respectively. This type of high intrinsic thermal conductivity (λ) and excellent intrinsic self-healing performance film is expected to solve the problems of safety and service life of high-precision smart devices.

研究领域: 材料科学 · 高分子化学
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ACS Applied Materials & Interfaces · 2020 · IF 8.758

Water-Enabled Room-Temperature Self-Healing and Recyclable Polyurea Materials with Super-Strong Strength, Toughness, and Large Stretchability

Zhen Shi,Jing Kang,Ling Zhang

The synthesis of polymeric materials that simultaneously possess multiple excellent mechanical properties and high-efficient self-healability at room temperature is always a huge challenge. Here, we report the synthesis of a transparent polyurea material that can self-heal at room temperature with the aid of water and, meanwhile, has multiple remarkable mechanical performances, including super-high strength, excellent toughness, and large stretchability. Thanks to the synergistic enhancement of both dynamic imine bonds and hierarchical hydrogen bonds within the networks, the resulting polyureas have a world-record tensile strength of 41.2 MPa when compared with other polyurethanes that can self-heal at room temperature and, at the same time, a large breaking strain of 823.0% and a superior toughness of 127.2 MJ/m3. Besides the influence of imine bonds, the mechanical properties of the polyureas are also strongly related to the density and strength of the hierarchical hydrogen bonds within the polyurea networks, and these two factors could be finely controlled by adjusting the mass ratio of the soft segments with different chain lengths and the types of diisocyanates used for polyurea synthesis, respectively. More importantly, the highly dynamic characteristic of both imine bonds and hierarchical hydrogen bonds within the polyureas endows the materials with repeated water-enabled room-temperature self-healing capacity with a high healing efficiency of 92.2%. Moreover, the polyureas can also be recycled or remolded under mild conditions by the hot-pressing or dissolution/casting process. The synthesized polyureas also show great potential in damping applications with a loss factor larger than 0.3 over the temperature range from 12 to 75 °C. It is believed that polyureas with super-high and well-tunable mechanical properties and high-efficient room-temperature self-healing ability have great potential to substitute traditional irreparable polymers in diverse practical applications.

CAS / MDL: 4098-71-9
研究领域: 材料科学 · 化学工程
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Journal of Environmental Chemical Engineering · 2024 · IF 7.4

Preparation and flotation-flocculation performance evaluation of hydrophobic modified PEI for produced water treatment

Shijie Tang,Yilin Lu,Qian Xu,Zhiping Chen,Ming Duan,Shenwen Fang

Imine bond is a kind of dynamic covalent bonds, in this paper, hydrophobic chain was introduced into polyethyleneimine (PEI) through imine bond, and a series of hydrophobic modified PEI were synthesized as flocculants for flotation-flocculation treatment of produced water. The hydrophobic modified PEI had much better flotation-flocculation performance than that of PEI. When the concentration was 20 mg/L and treatment was 10 min, the best hydrophobic modified PEI had the turbidity reduction rate of more than 95 %. Especially, in a short period of time, the flocs formed by the hydrophobic modified PEI can have a great decrease in adhesiveness under pH=4 due to the dissociation of imine bonds, which is good for the produced water treatment because the viscous flocs can be effectively processed. In addition, the mechanism study showed that the hydrophobic modified PEI can adsorb on the surfaces of bubbles and oil droplets to improve the collision efficiency and adhesion efficiency between bubbles and oil droplets, thus possessing good flotation-flocculation performance. This paper provides a novel degradable flocculant for produced water treatment.

研究领域: 环境科学 · 化学工程
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EUROPEAN POLYMER JOURNAL · 2025 · IF 6.3

Fully biobased epoxy vitrimer from resorcinol diglyceryl ether, vanillin, and 1,10-diaminodecane

Long-Yang Zhan,Ping Li,Yi-Dong Li,Yin Ran,Jian-Bing Zeng

Biobased epoxy vitrimers (BEVs) offer a promising solution to the recyclability and resource challenges associated with traditional epoxy thermosets. However, numerous existing BEVs suffer from inadequate properties or complex fabrication processes. Herein, we present a fully biobased, high-performance epoxy vitrimer synthesized from renewable and commercially available feedstocks: resorcinol diglyceryl ether (DGER), vanillin (VAN), and 1,10-diaminodecane (DDA). A dynamic imine crosslinker (DIC) was synthesized from VAN and DDA, which then underwent solvent-free and catalyst-free melt curing with DGER to form the BEV. Detailed studies of the curing kinetics of DGER-DIC and the properties of the resulting BEV were conducted, with comparisons to a control fossil-based epoxy vitrimer made from bisphenol A diglycidyl ether (DGEBA) and DIC. The DGER-DIC system showed a curing activation energy of 62.43 ± 3.73 kJ·mol –1 , slightly lower than DGEBA-DIC’s 67.71 ± 2.38 kJ·mol –1 . The BEV exhibited excellent mechanical properties, featuring a tensile strength amounting to 69.23 MPa and a Young’s modulus at 1.91 GPa, along with high thermal stability. The imine bonds provided fast stress relaxation, self-healing performance, and excellent reprocessability, with tensile strength recovering over 90 % after multiple processing cycles. These properties rival those of the DGEBA derived epoxy vitrimers, highlighting the potential of DGER as a sustainable alternative for creating recyclable epoxy thermosets.

CAS / MDL: 6683-19-8
研究领域: 材料科学 · 可持续化学
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JOURNAL OF MOLECULAR STRUCTURE · 2025 · IF 4.7

Construction of Covalent Triazine Frameworks (CTFs) Based on Imine Bonds for Efficient Adsorption of Hg2+ from Water

Yingbo Zhao,Fanrui Zhou,Kun Liang,Chunhua Wu,Xiaoping Rao,Qian Chen

In this study, a novel imine bond-based covalent triazine framework (CTF) with triazine groups as its backbone, designated as SWFU-CTFs-101 CTFs, was synthesized and utilized for the adsorption of Hg 2+ in an aqueous solution. The quasi-secondary kinetic model and Langmuir model indicate that the capture of Hg 2+ by the SWFU-CTFs-101 is a chemisorption process in a monomolecular layer. The maximum adsorption capacity of the material was determined to be 148.33 mg/g at a solid-liquid ratio of 1 mg/mL, an initial concentration of Hg 2+ of 400 mg/L, a pH of 6.0 and a temperature of 25°C. The adsorption mechanism of SWFU-CTFs-101 was elucidated by integrating experimental results, spectroscopic properties (SEM and XPS, etc.), and density functional theory (DFT) calculations. Notably, the adsorption capacity of SWFU-CTFs-101 in water remained largely stable after four cycles of recycling, indicating its promising potential for future practical applications.

研究领域: 材料科学 · 环境科学 · 化学工程
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COMPOSITES PART B-ENGINEERING · 2021 · IF 9.078

Controlling degradation and recycling of carbon fiber reinforced bismaleimide resin composites via selective cleavage of imide bonds

Qi Zhao,Xudong Li,Zishang Tian,Hui Ma,Xianglin Hou,Yingxiong Wang,Yuqi Wang

Carbon fiber reinforced bismaleimide resin (CF/BMI) composites are widely used in aerospace field due to their high thermal stability, chemical resistance and excellent mechanical properties . With the large-scale application of CF/BMI composites, it is inevitable to produce a lot of solid wastes, which have a serious impact on the environment, so people have to recycle waste CF/BMI composites. In view of the physical and chemical properties of BMI resin, we developed a green and friendly chemical recovery method of CF/BMI composites by selectively breaking imide bonds for controlled chemical degradation of BMI resin. In 5 wt% NaOH/H 2 O reaction system, the controlled chemical degradation of CF/BMI composites can be realized by selective cleavage of imide bonds, and the 4,4′-Diaminodiphenyl methane (DDM) and 2,2′,2″,2‴-((methylenebis(4,1-phenylene))bis(azanetriyl))tetrasuccinic acid (MBTA) can be recovered, and the carbon fiber (CF) can be recycled at the same time. Under the optimal reaction conditions, the yields of DDM and MBTA reached 6.7 wt% and 27.9 wt% at 180 °C for 8 h, respectively. Meanwhile, CF in CF/BMI composites can be completely recovered, and the tensile strength of recovered carbon fiber (rCF) is about 97.6% of that of virgin carbon fiber (vCF). This work provides a very promising strategy for the recycling of CF/BMI composites. The high value-added CF and chemicals (DDM and MBTA) can be recovered by controlled degradation of CF/BMI composites via selective cleavage of imide bonds.

研究领域: 材料科学 · 环境科学
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