Journal of Cleaner Production
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2025
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IF 10
Kuiling Wei,Xuejuan Cao,Yan Wu,Boming Tang,Bailin Shan,Xinqiang Zhang
In recent years, self-healing waterborne polyurethanes (SWPUs) with stimuli-responsive properties have attracted increasing attention. It is critical that dynamic crosslinking networks are designed to respond to appropriate stimulus. In this work, the effects of disulfide bonds, acylhydrazone bonds, and intrinsic hydrogen bonding on the mechanical properties, self-healing performance, and degradation behavior of SWPUs were explored. Initially, disulfide bonds were introduced into the crosslinked networks through a simple chemical modification of cystamine dihydrochloride, providing a cost-effective alternative to typical disulfide bond monomers. Subsequently, bio-based vanillin was used to cap isocyanate groups at ratios of 0.25, 0.5, 0.75, and 1.0, creating reactive sites for the condensation of diacylhydrazine with carbonyl groups. By adjusting the end-capping ratios, varying concentrations of acylhydrazone bonds were incorporated into the networks. The results indicated that increasing the end-capping ratio led to >83.4 % self-healing efficiency of SWPUs under both thermal and acidic conditions. The disordered hydrogen bonds improved the fracture strength of SWPUs, while the ordered hydrogen bonds enhanced the stiffness during stretching. In addition, the degradation test results revealed that SWPU was fully decomposed in a THF solvent (2-mercaptoethanol/deionized water/THF = 2/2/8, volume ratio). This excellent degradability is primarily attributed to the combined effects of imine hydrolysis, dynamic disulfide bonds, and copolymer fragmentation at single bonds near the carbonyl groups. This work presents a novel approach for designing polyurethane elastomers with multiple dynamic adaptive networks, offering the potential for low-cost production and cleaner preparation.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
EUROPEAN POLYMER JOURNAL
·
2021
·
IF 4.598
Liyuan Qiao,Chengde Liu,Cheng Liu,Lishuai Zong,Hongjian Gu,Chenghao Wang,Xigao Jian
Smart hydrogels have wide potential in biological field owing to their self-healing property, pH or temperature sensitivity. However, the preparation of smart hydrogels often requires complicated synthesis process, and the single functionality of hydrogels might limit their application. To solve these problems, we developed a self-healing, pH-sensitive and shape memory hydrogel of poly (diacetone acrylamide- co -acrylamide -co -acrylic acid)/alginate (PDAAc-A), taking advantage of the Schiff-base reaction and the hydrogen bonding interaction in a one-step method. The tensile modulus, fracture stress, fracture strain and toughness of the developed PDAAc-A3 hydrogel are 0.021 MPa, 0.013 MPa, 7.5 mm/mm and 0.07 MJ/m 2 , respectively. The dynamic and reversible acylhydrazone and hydrogen bonds endow hydrogels with self-healing property and pH-sensitive gel-sol transformation ability. The tensile tests demonstrate that the self-healing efficiency of hydrogel could reach up to 85% after about 30 min. Furthermore, PDAAc-A hydrogel exhibits pH-sensitivity during drug release. In PBS solution with pH value of 5, the hydrogel shows the fastest drug release rate and the highest drug release ratio, which is near 100% after about 4 h. Moreover, in 1 M ferric chloride solution, the shape memory time, shape memory ratio and shape recovery ratio of the resultant hydrogel are 2 min, 100% and 100%, respectively.
研究领域:
材料科学
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生物医学工程
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DOI
高影响因子
CONSTRUCTION AND BUILDING MATERIALS
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2024
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IF 7.4
Yanheng He,Tianwei Zhang,Ming Zeng,Hao Duan,Bing Zhang,Jianying Yu
To prepare SBS modified asphalt (SMA) waterproofing membrane with excellent self-healing performance, in this paper, four self-healing agents (ASHA-A, ASHA-B, ASHA-C, ASHA-D) with acylhydrazone bonds and carbon-carbon double bonds (C C) were synthesized, and were used to prepare self-healing SMA waterproofing membranes (SSMA-A, SSMA-B, SSMA-C, SSMA-D). The effects of ASHAs with different structures on the structure, high and low temperature properties, joint peel strength and self-healing performance of SSMAs were investigated. The Fourier transform infrared spectroscopy and fluorescence microscope results showed that acylhydrazone bonds of ASHAs were introduced into the chains of SBS molecules, and the SBS in SSMAs occurred crosslinking through the C C of ASHAs and SBS, the crosslinked network structures of SBS in SSMA-C and SSMA-D were denser and more complete because ASHA-C and ASHA-D contained more C C involved in the crosslinking reaction. The softening point and low temperature flexibility of SSMAs were enhanced by the formation of the SBS crosslinked network structure, and the optimum dosage of ASHAs was 0.6%. The joint peel strength of SSMA-A, SSMA-B, SSMA-C and SSMA-D increased by 26.68%, 31.25%, 49.52% and 56.97% compared to SMA. The introduction of acylhydrazone bonds with reversible fracture and rearrangement significantly improved the crack self-healing performance of SMA, the impermeability times of SMA, SSMA-A, SSMA-B, SSMA-C and SSMA-D were 13.28 min, 37.29 min, 42.53 min, 53.34 min and 59.67 min after self-healing at 40℃ for 8 h, which indicated that ASHA-D with benzene ring and multiple C C had the best improvement in self-healing performance of SMA.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE
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2024
·Vol. 59
·期 26
·12111-12127
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IF 3.5
Zhao Yanna,Bai Xiaowei,Zhang Yingying,Wang Yuqi,Huang Yuqing,Hou Wentong
Acylhydrazone bonds can participate in dynamic exchange reactions under acid-stimulated conditions, and disulfide bonds can participate in dynamic exchange reactions under thermally stimulated conditions. It is of great significance to prepare epoxy vitrimer that can rapidly self-repair under acid and thermal stimulation conditions. In this paper, vanillin was used as raw material, and monomer (VAN-AD) containing acylhydrazone bond was synthesized by reaction with adipic dihydrazide. Then, VAN-AD and 4-aminophenyl disulfide (SS) were cured together with glycerol triglycidyl ether to prepare an epoxy vitrimer with acylhydrazone and disulfide dual dynamic covalent bonds. Where VAN-AD provides some of the flexible chain segments and acylhydrazone bonds and SS provides the aromatic phenyl and disulfide bonds. The material was prepared in a simple process and under mild condition, and the properties of the material were optimized by changing the ratio of VAN-AD to SS. The T g of the material was 50 °C when the ratio of SS was the highest, the thermal stability was enhanced with the increase of the ratio of SS, and the maximum tensile strength up to 50.9 MPa, and the material can be completely degraded by DMF with 5% HCl. It is worth noting that the material shows rapid self-healing properties under acid-heat conditions, self-healing rates up to 97.37%, and the tensile strength can reach 26 MPa after repair. The material can be successfully remodeled by hot pressing for 1 h at 140 °C and 10 MPa. Graphical abstract
研究领域:
材料科学
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化学工程
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DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE
·
2019
·Vol. 54
·期 11
·8814-8828
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IF 3.442
Qiao Liyuan,Liu Chengde,Liu Cheng,Yang Liquan,Zhang Manxia,Liu Wentao,Wang Jinyan,Jian Xigao
Dialdehyde-terminated PEG (PEG–CHO) and adipic dihydrazide-modified alginate (ALG-ADH) was developed to provide aldehyde and hydrazide active sites, respectively, and thus to obtain dynamic acylhydrazone bonds, which endow alginate hydrogel with excellent self-healing property. Different concentrations of cross-linking agent have been added, and their influence on the structure, morphology, mechanical properties and self-healing performance has been evaluated. The gelation kinetics, shear performance and compressive property have been investigated in detail. The hydrogel with 5% cross-linking agent exhibited the highest mechanical performance, with the shear modulus of 0.234 MPa and compressive modulus of 0.288 MPa. Due to dynamic acylhydrazone and multiple hydrogen bonds, the hydrogels have demonstrated excellent self-healing properties. After self-healing process, the hydrogel has retained 84.4% of the original tensile modulus. The as-prepared alginate hydrogel was molded into different shapes to exhibit the excellent plasticity. Moreover, when tetracycline hydrochloride was loaded into the hydrogel system as a model drug, the modified alginate hydrogel demonstrated the fastest drug release rate at pH = 7.4. It is suggested that the self-healing alginate hydrogel has a great potential in drug delivery, such as targeted drug release in intestinal treatment.
研究领域:
材料科学
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生物医学工程
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DOI
高影响因子
POLYMERS FOR ADVANCED TECHNOLOGIES
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2022
·Vol. 33
·期 8
·2528-2541
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IF 3.348
Lijun Chen,Sui Wang,Zhiyong Guo,Yufang Hu
Hydrogels with excellent self-healing properties have specific applications in smart polymer materials, but they often do not have excellent mechanical properties, or the preparation process of hydrogels is too complicated. Here, we prepared a multi-functional intelligent hydrogel using a simple water bath one-pot method through the synergistic effect of dual dynamic cross-linked agents, including acylhydrazone bonds (the first cross-linked agent) and borate ester bonds (the second cross-linked agent), at the same time hydrogen bonds provided physical interaction. The hydrogel exhibited excellent self-healing ability (up to 91%) and extraordinary mechanical strength (tensile stress 173.1405 kPa and hysteresis energy of 1.8659 MJ m −3 ). The research used chemical cross-linked (acylhydrazone bonds and borate ester bonds) and physical cross-linked (hydrogen bonds). The prepared hydrogel had the dual advantages of excellent self-healing performance and high mechanical strength. The hydrogel can be used in smart materials, such as working pressure tissues and sensing materials that require a certain degree of mechanical strength and self-healing properties, and also provides a design strategy for preparing hydrogels with high mechanical strength and excellent self-healing properties.
研究领域:
材料科学
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生物医学工程
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产品关联
DOI
高影响因子
International Journal of Polymeric Materials and Polymeric Biomaterials
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2023
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IF 3.2
Jie Mao,Yalei Liu,Lijun Chen,Sui Wang
In this paper, PVA/BDA/ADH gels with good mechanical properties and self-healing properties were prepared using polyvinyl alcohol (PVA), 4,4-biphenyldicarboxaldehyde (BDA), and adipic dihydrazide (ADH) as raw materials. The hydrogel network achieves chemical-physical double cross-linking through acylhydrazone bonds and hydrogen bonds. The as-prepared PVA/BDA/ADH gels have good mechanical properties (the tensile stress of PVA/BDA/ADH gels is about 2 times that of pure PVA hydrogel) due to chemical and physical double cross-linking. It also has good self-healing properties under external conditions. Compared with pure PVA hydrogel, PVA/BDA/ADH gels have more stable self-healing properties.
研究领域:
材料科学
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生物材料
✓ 已验证
产品关联
DOI
高影响因子
POLYMER
·
2024
·
IF 4.1
Xiaoshu Wei,Xin Dong,Meiying Huang,Zhipeng Zhou,Zihao Liang,Yuyao Li,Yonghang Yang,Jiaxing Lu,Zhilv Wang,Changye Zhan,Wei Liu,Zhikun Zheng
The central feature of covalent organic frameworks (COFs) is crystallinity which is conducive to forming a uniform pore structure . However, synthesis of highly crystalline COFs based on stable covalent bonds remains formidable task. In this paper, a highly crystalline acylhydrazone COF-BD was synthesized in aqueous phase. The synthesis mechanism was proposed that the protonated hydrazide monomers dissolved in aqueous phase reacted with aldehyde monomers by deprotonation into the micellar. By investigating the effects of experimental parameters on the crystallinity of COF-BD, it was founded that under C9–COONa as surfactant , 80 °C, and 1.0 eq acetic acid as catalyst, acylhydrazone COF-BD with good crystallinity could be prepared. To prove the extensibility of this method, another acylhydrazone COF was prepared successfully.
研究领域:
材料科学
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化学
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产品关联
DOI
高影响因子
Polymer Chemistry
·
2024
·Vol. 15
·期 22
·2253-2264
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IF 4.1
Yunsheng Xu,Chonglin Liu,Yanying Zhao,Xianming Zhang,Minna Hakkarainen
Acylhydrazone linkages are appealing for the design of covalent adaptable networks (CANs) due to their reversible nature and ease of formation from readily available starting materials. However, acylhydrazone CANs typically exhibit dynamic behavior within a limited temperature range due to their slow exchange rate. Here, vanillin was modified by a two-step reaction involving allylation and imination, followed by photo-curing with a four-armed thiol to fabricate acylhydrazone CANs. The dynamic behavior of these CANs could be controlled by adjusting the amount of p-anisidine (AD) organocatalyst. A model compound reaction revealed that the addition of a catalyst transforms the mechanism of acylhydrazone exchange from a 2 + 2 cycloaddition reaction to a nucleophilic addition reaction, effectively lowering the energy barrier of the intermediate state. CANs with higher amounts of AD catalyst exhibited shorter relaxation times and lower activation energies, thereby expanding the reprocessing temperature window and enhancing the recovery ratio of tensile stress after reprocessing. All the fabricated CANs demonstrated ready chemical recyclability in acidic or AD/DMSO solutions at 80 °C, following two different mechanisms depending on the reaction medium. These findings pave the way to photo-curable renewable acylhydrazone CANs with adjustable viscoelastic properties and mechanical and chemical recyclability enabled by rapid dynamic exchange reactions.
研究领域:
材料科学
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化学工程
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产品关联
DOI
高影响因子
ACS Applied Bio Materials
·
2019
·
IF 0
Yanping Tong,Zhaochuang Wang,Yan Xiao,Wei Liu,Jinghao Pan,Yan Zhou,Meidong Lang
The emerging tide of hydrogels in biomedical fields drives them to possess good biocompatibility, tunable mechanical properties, and fast gelation process. Herein, a composite hydrogel containing copolypept(o)ides and functional polysaccharides was constructed through dynamic acylhydrazone linkages. First, a series of peptide–peptoid copolymers were synthesized by ring-opening polymerization of sarcosine (Sar) and l-glutamic acid γ-benzyl ester (BLG) N-carboxyanhydrides (NCAs). The benzyl groups of BLG units were substituted with hydrazide groups through ester–amide exchange aminolysis reaction. The statistical copolymer of poly(sarcosine-co-glutamate-hydrazide) (P(Sar-co-GH)) was chosen as an optimized precursor due to its excellent water solubility and gel-forming ability with aldehyde-modified sodium alginate (OSA). Moreover, cellulose nanocrystals (CNCs) were prepared as nanofillers to reinforce the P(Sar-co-GH)-OSA hydrogel. We demonstrated that the copolymer sequences and composition contents made a difference to the properties of the formed hydrogels by variation of the cross-linking density. The dynamic acylhydrazone bonds endowed hydrogels with pH responsiveness and reversible networks. The NIH/3T3 cells encapsulated in the hydrogels maintained high viability and proliferation abilities, indicating that the nanocomposite hydrogels could be explored to fabricate a customized responsive drug delivery system or cell scaffolds for tissue engineering.
研究领域:
生物材料学
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生物医药工程
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产品关联
DOI
PubMed
JOURNAL OF POLYMER SCIENCE
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2023
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IF 3.4
Yanna Zhao,Yuqing Huang,Wentong Hou,Ting Zhang,Yingying Zhang,Yuqi Wang,Xiaowei Bai
Vitrimer films containing acylhydrazone bonds are synthesized in two steps. Bio-based vanillin and adipate dihydrazide are used to prepare diols containing acylhydrazone bonds in one step, which are introduced into the reaction system of vitrimer to obtain the final films. The process is concise and easy to operate. By utilizing the rigid structure of vitrimer films and introducing dynamic acylhydrazone bonds, the obtained vitrimer films exhibit strong mechanical strength (maximum tensile strength of 27.10 MPa and maintaining up to 185.52% of the original breaking strength), excellent self-healing property (tensile strength of 26.26 MPa after 12 h of primary self-healing and 5.24 MPa after 12 h of secondary self-healing), and rapid shape memory property (recovery time of about 2 min), strong acid and alkali resistance (not dissolved within 24 h), good thermal stability (no decomposition occurs below 160 °C), and high storage modulus (reaches 1087 MPa). These comprehensive benefits yield a certain reference for the preparation of vitrimer materials with prime properties. Graphical
研究领域:
材料科学
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化学工程
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DOI
高影响因子
JOURNAL OF WUHAN UNIVERSITY OF TECHNOLOGY-MATERIALS SCIENCE EDITION
·
2023
·Vol. 38
·期 4
·929-937
·
IF 1.6
Lu Mengli,Huang Lihua,Zhan Siwen,Li Juncan,Qiu Tong,Yang Mengjia,Li Jie,Tong Miao,Zhang Xueqiong,Shi Chuan
An acid-sensitive delivery system based on acylhydrazone bond was developed for high loading and efficient delivery of doxorubicin. Doxorubicin(DOX) was covalently combined with dihydrazide adipate to form acid-sensitive hydrazone bond based on Schiff base reaction, then the intermediate was covalently combined with carboxymethyl chitosan through amide bond to form polymeric prodrugs, and nanoparticles were formed through self-assembling. Moreover, the structural and particle properties of CMCS-ADH-DOX were characterized by ultraviolet visible near infrared spectrophotometry (UV), nuclear magnetic resonance spectroscopy ( 1 H-NMR), fourier transform infrared spectroscopy (FT-IR), dynamic light scattering (DLS), and transmission electron microscopy (TEM). The mean diameter of the self-assembled nanoparticles is 165 nm, while the morphology is a relatively uniform spherical shape. Moreover, these DOX-loaded nanoparticles showed pH-triggered drug release behavior. Compared with free DOX, CAD NPs showed lower toxic side effects in L929 cells and similar toxicity in 4T1 cells. The experimental results indicate that the CMCS-ADH-DOX nanoparticles may be used as an acid-sensitive targeted delivery system with good application prospect for cancer.
研究领域:
药剂学
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肿瘤学
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生物材料学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）