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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Synthesis of an aromatic amine derived from biomass and its use as a feedstock for versatile epoxy thermoset

Jiahui Li,Zhihuan Weng,Qi Cao,Yu Qi,Bowen Lu,Shouhai Zhang,Jinyan Wang,Xigao Jian

Innovative bio-based monomers and polymers are required as substitutes for limited fossil resources. Aromatic amines as an important class of chemicals are currently mostly formulated from petroleum. In this paper, a guaiacol derivative aromatic amine (5-aminoguaiacol) was designed and successfully synthesized, which was employed together with vanillin to build a high bio-based bisphenol compound. Following by glycidylation and cross-linking with 4,4′-diaminodiphenyl methane (DDM), we presented an epoxy resin network (GV-EP/DDM) bearing dynamic Schiff base bonds with high glass transition temperature of 220 °C, char yield (in N 2 at 800 °C) of 44.9%, storage modulus at 30 °C of 3602 MPa, and Young’s modulus of 4489 MPa, which was 33 °C, 2.5-fold, 38% and 28% higher than those of bisphenol A epoxy resin, respectively. Furthermore, the introduction of Schiff base structure endowed the GV-EP/DDM system with shape memory, degradability, reprocessability at 230 °C under 10 MPa, as well as satisfactory antibacterial property. Notably, the higher crosslinking density made GV-EP/DDM have stronger acid resistance than the other epoxy resins with Schiff base bonds. This work provides a feasible toolbox for production of bio-based aromatic amine compounds, and a strategy to construct high performance and versatile bio-based polymer materials.

CAS / MDL: 106-89-8
研究领域: 材料科学 · 有机化学
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CARBOHYDRATE POLYMERS · 2020 · IF 7.182

Self-healing hyaluronic acid hydrogels based on dynamic Schiff base linkages as biomaterials

Shangzhi Li,Minjie Pei,Tingting Wan,Hongjun Yang,Shaojin Gu,Yongzhen Tao,Xin Liu,Yingshan Zhou,Weilin Xu,Pu Xiao

Natural hydrogels are widely investigated for biomedical applications because of their structures similar to extracellular matrix of native tissues, possessing excellent biocompatibility and biodegradability. However, they are often susceptible to mechanical disruption. In this study, self-healing hyaluronic acid (HA) hydrogels are fabricated through a facile dynamic covalent Schiff base reaction. Dialdehyde-modified HA (AHA) precursor was synthesized, and then the AHA/cystamine dihydrochloride (AHA/Cys) hydrogels were formed by blending AHA and Cys at acidic pH levels. By varying Cys to AHA ratio, the hydrogel morphology, swelling and kinetics of gelation could be controlled. Gelation occurred fast, which was predominantly attributed to Schiff base reaction between the dialdehyde groups on AHA and amimo groups on Cys. The hydrogel exhibited improved mechanical properties with increase in Cys content. Furthermore, due to dynamic imine bonds, this hydrogel demonstrated excellent self-healing ability based on the stress after mechanical disruption. Also, it was found to be pH-responsive and injectable. Taken together, this kind of hyaluronic acid hydrogel can provide promising future for various biomedical applications in drug delivery, bioprinting, smart robots and tissue regeneration.

CAS / MDL: 870-46-2
研究领域: 生物材料学 · 组织工程学
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COMPOSITES SCIENCE AND TECHNOLOGY · 2014 · IF 3.633

Composite aerogels based on dialdehyde nanocellulose and collagen for potential applications as wound dressing and tissue engineering scaffold

Tianhong Lu,Qing Li,Wenshuai Chen,Haipeng Yu

Nanocellulose and collagen are all natural polymer materials, and their combination could expand the mode and scope of applications. Employing a mild chemical purification together with the subsequent ultrasonic treatment, the nanocellulose fibers (NCFs) were isolated from wood powder, and were then oxidized into dialdehyde NCFs by sodium periodate, which offers active sites for introducing collagen. The dialdehyde NCFs and collagen were crosslinked together through the bonds of Schiff base . The dialdehyde NCFs act as matrix to guide the growth of collagen, and through the chemical crosslinkage, collagen grew along dialdehyde NCFs and formed the composite aerogels . The as-prepared NCF/collagen composite aerogels, consisting of the membranes interwoven by NCF/collagen composite fibers , exhibited low-densities between 0.02 and 0.03   g   cm −3 , high-porosities ranged from 90% to 95%, and strong water absorption up to 4000%. The aerogels also exhibited good biocompatibility as well as high level of cell activity and proliferation, which may be suitable for biological wound dressings and tissue engineering scaffolds.

研究领域: 生物材料学 · 组织工程 · 伤口护理
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Journal of Materials Chemistry A · 2020 ·Vol. 8 ·期 14 ·6757-6767 · IF 11.301

Developing visible-light-induced dynamic aromatic Schiff base bonds for room-temperature self-healable and reprocessable waterborne polyurethanes with high mechanical properties

Wuhou Fan,Yong Jin,Liangjie Shi,Rong Zhou,Weining Du

Herein, a novel type of visible-light-induced dynamic covalent bond was developed based on aromatic Schiff base (ASB) bonds, and the prepared waterborne polyurethanes containing dynamic ASB bonds (ASB-WPU) exhibited a desirable self-healability (healing efficiency of 83.8%) after healing under a commercial LED table lamp for 24 hours (temperature of ∼25 °C). Meanwhile, high mechanical properties (tensile stress of 14.32 MPa and toughness of 64.80 MJ m−3) could also be obtained, demonstrating a good balance of room-temperature self-healability and high mechanical properties in our polymers. The imine metathesis of ASB bonds and the H-bonded interactions between urethane groups could afford the ultimate healing result simultaneously, in which the imine metathesis of ASB bonds triggered by visible light is the main factor. Furthermore, these ASB-WPU polymers could also be reprocessed under visible light with well recovered mechanical properties. We envision that this elaborate design philosophy, based on the readily available, clean, safe and easily manipulable visible light, could provide inspiration for preparing room-temperature self-healable and reprocessable polymers with high mechanical properties, which are urgently needed for next-generation smart materials.

研究领域: 材料科学 · 高分子化学
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COLLOIDS AND SURFACES B-BIOINTERFACES · 2021 · IF 5.268

Insight into the mechanism and formation process of bioinspired poly(amino acid)/polyphenol capsules engineered with fast pH switchable permeability

Shaoyin Wei,Daozhen Zhou,Jianghui Qin,Bo Peng,Xingjie Zan

Capsules have hollow cores and closed wall structures, and they have attracted considerable interest due to their wide applications and significance in life science. The engineering process of bioinspired capsules and related applications have earned heavy concerns. However, the mechanism of capsule formation is often ignored. Herein, based on polyornithine (POR) and tannic acid (TA), two facile strategies to engineer bioinspired capsules were proposed, and the formation mechanisms were deeply explored. We found that the oxidized state of TA had a profound influence not on the thickness or permeability of the formed capsule but on the mechanism and generation process. Compared to TA/POR capsules produced from TA without oxidization ( TA/POR), capsules produced from TA with preoxidization ( o TA/POR) had thicker shells with higher impermeability. The dominant construction mode in the shells of TA/POR capsules was electrostatic interactions but became Schiff base bonds in o TA/POR capsules. The permeability of o TA/POR displayed pH reversibility and strong pH dependence, with 100% permeability at lower pH and 100% impermeability at pH 7, completing loading/releasing kinetics in minutes at pH 4. We believe these findings contribute to knowledge of bioinspired capsules from engineering processes and formation mechanisms, extending their applications in various fields, such as in drug delivery, artificial cells, and sensors.

研究领域: 材料科学 · 化学 · 生物技术 · 药学
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GIANT · 2023 · IF 7

A polymyxin and cellulase based smart hydrogel for localized infection treatment and biofilm eradication

Yongxin Yang,Yunqing Gu,Kunyu Chen,Jiajia Luo,Zijuan Cheng,Yiyun Cheng,Jingjing Hu

Polymyxins are credited as the last line of defense against the clinical multi-resistant Gram-negative pathogen infections. However, their clinical use is limited by high nephrotoxicity and neurotoxicity, and less effectiveness against mature biofilms. In this work, the polymyxins including polymyxin B and polymyxin E were crosslinked with oxidized dextran via the acid labile Schiff base linkage. The generated hydrogel can release the polymyxins upon bacterial infection in an on-demand manner, which may alleviate adverse effects of the antibiotics. Moreover, a multifunctional hydrogel is generated by introducing the enzyme cellulase into the polymyxin hydrogel via the same Schiff base chemistry. The prepared gel can effectively degrade the mature biofilm, sensitizing the polymyxins in the treatment of biofilm-associated infections both in vitro and in vivo . This study provides an effective strategy to reduce the side effects of polymyxins and enhance their sensitivity against the mature biofilm-associated localized infections.

研究领域: 药学 · 生物医学工程 · 传染病学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2025 · IF 8.5

Vanillin-mediated green synthesis of polyacrylic acid/chitosan dual-network hydrogels with antibacterial properties and enhanced mechanical performance

Xiao Sun,Yangyang Sun,Baoxia Hou,Qun Zhang,Weikun Jiang,Huimei Wang,Yu Liu

The polyphenol–metal catalytic scheme plays a crucial role in the synthesis of polyacrylic acid (PAA) hydrogels. Herein, vanillin (VA) not only initiates dynamic redox reactions with Fe 3+ to accelerate the polymerization of acrylic acid but also forms Schiff-base bonds with chitosan (CS), thereby facilitating the formation of a CS molecular network. Consequently, VA enables rapid, environmentally friendly synthesis of dual-network hydrogels comprising PAA and CS. Experimental results demonstrate that the products obtained using these hydrogels possess good mechanical properties, adhesion properties, self-healing ability, and antibacterial properties. Under the optimal experimental conditions, these hydrogels exhibit a fracture elongation of 810.30 % and a tensile strength of 202.14 kPa. Introducing phytic acid improves the flexibility and adhesiveness (98.3 kPa for porcine skin) of the hydrogel samples. Moreover, these hydrogels exhibit notable antibacterial properties in the inhibition of both Escherichia coli and Staphylococcus aureus . When used as wearable sensors, PAA–CS hydrogels can monitor human movements in real time while achieving high sensitivity and rapid response. This self-catalytic system based on polyphenol–metal redox reactions offers a green and efficient approach for preparing multifunctional hydrogels.

研究领域: 高分子化学 · 材料科学 · 生物医学工程 · 绿色化学 · 抗菌材料
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ACS Applied Polymer Materials · 2025 · IF 4.7

Dynamic Schiff Base Bonds Enable Recyclable, High-Toughness Vanillin Epoxy Resins via Micro–Nano-Phase Engineering

Songjie Xu,Likang Zhou,Junhao Fei,Meng Ma,Huiwen He,Yanqin Shi,Yulu Zhu,Si Chen,Xu Wang

Epoxy resins are widely used in composite materials due to their excellent thermal stability and mechanical properties. However, their covalent cross-linked networks prevent their recyclability, and the reliance on petroleum-based raw materials hinders sustainable development. Although the reversible cross-linking of biobased dynamic epoxy resins such as vanillin-Schiff base systems enables their recycling, the synergistic effect of high cross-linking density and rigid dynamic bonds leads to significant brittleness. To overcome these problems, this work proposes a strategy to achieve microphase separation via polarity modulation. Specifically, a m-xylylenediamine derivative that incorporates long alkyl chains was designed to react with a vanillin-based epoxy resin containing dynamic Schiff base bonds, resulting in the formation of chemically bonded micro/nanophase domains during curing. Results revealed that this strategy regulated the cross-linking density and improved the compatibility between the alkyl chains and epoxy cross-linked networks, endowing the biobased epoxy resin with 80% elongation at break and a remarkable tensile toughness of 12.8 MJ·m–3, which represents a 6.1-fold enhancement over conventional systems. The designed low-density cross-linked networks show dual advantages: facile acid-catalyzed degradation with full depolymerization in 5 h and supporting low-temperature reprocessing. Besides, the solvent resistance remains largely unaffected. In addition, glass fiber-reinforced composites prepared using the biobased epoxy resin exhibited outstanding interfacial bonding and degradation performance, with a fiber recycling rate exceeding 95%, demonstrating high strength, high toughness, and recyclability. This study offers a previously unexplored route toward achieving both high tensile toughness and recyclability in biobased epoxy resins used for glass fiber-reinforced composites.

研究领域: 高分子科学 · 材料工程 · 化学合成 · 复合材料 · 可持续化学
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Materials Express · 2024 ·Vol. 14 ·期 4 ·583-589 · IF 0.7

A thermo-sensitive hydrogel based on Schiff base linkages with antioxidant property

Luo Yao,Wu Wei-Gang,Tian Feng,Huang Jun

Excessive oxidative stress leading to a consequently chronic inflammation remains a challenging problem for wound healing, and developing biomaterials with outstanding antioxidant property has great practical significance for wound treatment. Herein, a thermo-sensitive hydrogel based on Schiff base linkages (Cur@HBC/OHA) was prepared, and the physicochemical properties and antioxidant activities in vitro were investigated. The excellent biocompatibility, enhanced antibacterial activity and increased DPPH scavenging rate indicated that the prepared Cur@HBC/OHA hydrogel is a promising biomaterial for tissue engineering applications.

研究领域: 生物材料科学 · 组织工程 · 药学
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INTERNATIONAL JOURNAL OF PHARMACEUTICS · 2021 · IF 5.875

Construction and antitumor properties of a targeted nano-drug carrier system responsive to the tumor microenvironment

Wenzhao Han,Junfeng Ke,Feng Guo,Fanwei Meng,Hui Li,Liping Wang

Doxorubicin (DOX) is one of the most commonly used and effective chemotherapy drugs among anthracyclines . An inherent limitation of DOX is its nonspecificity, which can cause serious side effects, thereby preventing the therapeutic use of high drug doses. In this study, we designed and created a simple nano-drug delivery system (PEG-MAF = P) with low biological toxicity that was responsive to the tumor environment. PEG-MAF = P was designed to self-assemble into nanospheres via control of a phenylalanine dipeptide (FF). The N-terminus of the peptide was linked to aldehyde groups at both ends of oxidized Pluronic F127 (F127-CHO) via Schiff bonds. The acidic environment surrounding the tumors was suitable for triggering the Schiff bonds, causing the nanospheres to disintegrate. The C-terminus of FF was connected to a ligand peptide, ATN-161, which was able to recognize cells expressing high levels of integrin α5β1 antigens both in vivo and in vitro . To prevent the impediment in drug release, PEG was linked via a matrix metalloproteinase-9 response peptide. Therefore, in an acidic tumor microenvironment containing MMP-9, PEG-MAF = P disintegrated and rapidly released the drug. PEG-MAF = P exhibited low cytotoxicity, high drug-loading rate, and excellent antitumor properties both in vivo and in vitro . Compared with free DOX, PEG-MAF = P-DOX reduced injury to normal tissues.

CAS / MDL: 25316-40-9 87413-09-0
研究领域: 药学 · 纳米技术 · 肿瘤学
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Materials Chemistry Frontiers · 2022 ·Vol. 6 ·期 9 ·1137-1149 · IF 8.683

Enhancement of intrinsic thermal conductivity of liquid crystalline epoxy through the strategy of interlocked polymer networks

Sheng Jie Yuan,Zhong Quan Peng,Min Zhi Rong,Ming Qiu Zhang

To enhance the intrinsic thermal conduction of liquid crystalline epoxy (LCE), a novel strategy based on interlocked polymer networks is proposed. Two cured versions of LCE respectively containing Schiff base bonds and Diels–Alder (DA) bonds are synthesized, and then well mixed in a co-solvent enabling topological reorganization of the single LCE networks via the reversible reactions of the built-in dynamic covalent bonds. The thermal conductivity of the interlocked LCE networks prepared according to the optimal formulation offered by orthogonal design is significantly increased in comparison with the parent single-LCE networks. Besides, although the thermal conductivity of the raw LCE employed in the current work is not that high and the mesogen monomer has the simplest structure, the interlocked networks are able to bring the liquid crystals into full play without changing the chemical structure of the mesogens, as characterized by the very high thermal conductivity per unit weight of liquid crystal. Further investigation of the underlying mechanism suggests that the synergy among the mesogens, the interlocked structure and the inter-component hydrogen bonds accounts for the promotion of heat transmission. Considering the easy access of the relevant chemicals and the simplicity of the materials preparation, the technology developed in the present work may have remarkable potential for future applications.

研究领域: 材料科学 · 高分子化学 · 热工程
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Journal of Materials Chemistry B · 2021 ·Vol. 10 ·期 4 ·562-570 · IF 6.331

Hyaluronic acid targeted and pH-responsive multifunctional nanoparticles for chemo-photothermal synergistic therapy of atherosclerosis

Shun Liu,Yun Zhao,Meili Shen,Yujiao Hao,Xiaodong Wu,Yixuan Yao,Yapeng Li,Qingbiao Yang

Atherosclerosis is a global disease with an extremely high morbidity and fatality rate, so it is necessary to develop effective treatments to reduce its impact. In this work, we successfully prepared a multifunctional drug-loaded nano-delivery system with pH-responsive, CD44-targeted, and chemical–photothermal synergistic treatment. Dendritic mesoporous silica nanoparticles capped with copper sulfide (CuS) were synthesized via an oil–water biphase stratification reaction system; these served as the carrier material and encapsulated the anticoagulant drug heparin (Hep). The pH-sensitive Schiff base bond was used as a gatekeeper and targeting agent to modify hyaluronic acid (HA) on the surface of the nanocarrier. HA coating endowed the nanocomposite with the ability to respond to pH and target CD44-positive inflammatory macrophages. Based on this multifunctional nanocomposite, we achieved precise drug delivery, controlled drug release, and chemical–photothermal synergistic treatment of atherosclerosis. The in vitro drug release results showed that the nanocarriers exhibited excellent drug-controlled release properties, and could release drugs in the weakly acidic microenvironment of atherosclerotic inflammation. Cytotoxicity and cell uptake experiments indicated that nanocarriers had low cytotoxicity against RAW 264.7 cells. Modification of HA to nanocarriers can be effectively internalized by RAW 264.7 cells stimulated by lipopolysaccharide (LPS). Combining CuS photothermal treatment with anti-atherosclerosis chemotherapy showed better effects than single treatment in vitro and in vivo. In summary, our research proved that H-CuS@DMSN-NC-HA has broad application prospects in anti-atherosclerosis.

研究领域: 纳米技术 · 药学 · 心血管疾病
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