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逆Diels-Alder反应
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY · 2023 · IF 10.9

Injection molding of highly filled microcrystalline cellulose/polycaprolactone composites with the aid of reversible Diels-Alder reaction

Ze Pu Wang,Wen Hong Ruan,Min Zhi Rong,Ming Qiu Zhang

To tackle the challenge of producing highly filled polymer composites using the traditional injection molding technique, which is characterized by the fairly high melt viscosity that makes mold filling difficult, the authors propose a solution based on dynamic covalent chemistry. As demonstrated by the proof-of-concept experiments, the 4-arm star-shaped polycaprolactone (PCL) oligomers and microcrystalline cellulose (MCC) are crosslinked by the reversible Diels-Alder (DA) bonds. The flowability of the compounds greatly decreases due to the dissociation of the intercomponent DA bonds at the retro-reaction temperature, and the networked architecture is reconstructed during cooling as a result of the forward DA reaction. Consequently, the high-loading MCC fillers are well distributed in the matrix and covalently bonded to the nearby PCL, forming a striking contrast to the control in which linear PCL acts as the matrix. The DA bonds crosslinked biodegradable PCL composites exhibit decent mechanical strength (20.7 MPa) even at the MCC fraction of 65 wt%, which is superior to those (5–12.2 MPa) of the highly filled PCL composites (with filler contents of 50–63.8 wt%) reported so far. The proposed approach has sufficient expansibility for the fabrication of the highly filled polymer composites constructed by other types of matrix and fillers.

CAS / MDL: 104676-09-7
研究领域: 材料科学 · 化学工程
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POLYMER COMPOSITES · 2021 ·Vol. 42 ·期 9 ·4289-4301 · IF 3.171

Self-healing interface of carbon fiber reinforced composites using a thermally reversible sizing agent

Xiaoqing Zhang,Sihui Liu,Zhuojian He,Caihong Lei

A thermally reversible sizing agent was prepared by directly mixing the furfurylamine-modified epoxy resin (FAE) and the maleimide-functionalized Jeffamine T403 (MAT), and it was used to impart self-healing ability at interface based on the reversible Diels–Alder reaction for potential application in carbon fiber composites. The surface characteristics of FAE/MAT-modified carbon fibers were investigated using scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and dynamic contact angle meter and tensiometer. The initial interfacial shear strength of modified carbon fiber composites and the multiple healings of the interface were investigated via a microbond test. The results demonstrated that the healing efficiency of the continuous and uniform FAE–MAT sizing layer functionalized carbon fiber composites was up to 93.8% for the first healing cycle. Furthermore, it is expected that the interface self-healing of carbon fiber reinforced composites can be achieved from research laboratory to industrial applications by this strategy.

CAS / MDL: 101-77-9
研究领域: 材料科学 · 复合材料工程
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Journal of Materials Chemistry B · 2024 ·Vol. 12 ·期 24 ·5848-5860 · IF 6.1

Peptide nanovaccine conjugated via a retro-Diels–Alder reaction linker for overcoming the obstacle in lymph node penetration and eliciting robust cellular immunity

Kuncheng Lv,Sheng Ma,Liping Liu,Hongyu Chen,Zichao Huang,Zhenyi Zhu,Yibo Qi,Wantong Song

Nanoparticles have been regarded as a promising vaccine adjuvant due to their innate immune potentiation and enhanced antigen transport. However, the inefficient infiltration into the lymph node (LN) paracortex of nanoparticles caused by subcapsular sinus (SCS) obstruction is the main challenge in further improvement of nanovaccine immune efficacy. Herein, we propose to overcome paracortex penetration by using nanovaccine to spontaneously and continuously release antigens after retention in the SCS. In detail, we utilized a spontaneous retro-Diels–Alder (r-D–A) reaction linker to connect poly{(2-methyl-2-oxazoline)80-co-[(2-butyl-2-oxazoline)15-r-(2-thioethyl-2-oxazoline)8]} (PMBOxSH) and peptides for the peptide nanovaccine construction. The r-D–A reaction linker can spontaneously break over time, allowing the nanovaccine to release free antigens and adjuvants upon reaching the LN, thereby facilitating the entry of released antigens and adjuvants into the interior of the LNs. We showed that the efficacy of the peptide nanovaccine constructed using this dynamic linker could be significantly improved, thus greatly enhancing the tumor inhibition efficacy in the B16-OVA model. This dynamic-covalent-chemistry-based vaccine strategy may inspire designing more efficient therapeutic vaccines, especially those that require eliciting high-amount T cell responses.

研究领域: 纳米技术 · 免疫学 · 药学 · 癌症研究
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EUROPEAN POLYMER JOURNAL · 2024 · IF 5.8

Multi-responsive self-healing behavior of polyurethane modified with photothermal and microwave conversion nanoparticles

Jiaofeng Ye,Shuanglong Chen,Libang Feng,Jianbin Zhang,Yanhua Liu,Danbin Zhu

Self-healing polyurethane used in architectural engineering often suffers from contradictory mechanical and self-healing properties, limited repair options and low repair efficiency. In this research, a series of self-healing polyurethane materials were manufactured by introducing Fe 3 O 4 , polydopamine (PDA) and Fe 3 O 4 @PDA nanoparticles into polyurethanes based on thermo-reversible Diels-Alder reaction. These nanoparticles endowed self-healing polyurethane with multiple responses to thermal, NIR and microwave. Consequently, the evident cracks were renovated quickly and repeatedly upon these excitations. Therefore, the nanoparticles not only improved the healing efficiency markedly, but also endowed polyurethane with multiple responsive self-healing ability. Interestingly, due to the synergistic interaction between photothermal effect, microwave effect, and rigidity of Fe 3 O 4 as well as photothermal effect and compatibility with organic matrix of PDA, Fe 3 O 4 @PDA-modified polyurethane was empowered with the most exceptional mechanical and self-healing properties. Results revealed that Fe 3 O 4 @PDA nanoparticles-modified polyurethane exhibited high mechanical properties such as strength, toughness and hardness as well as excellent multiple stimulus response self-healing performance. More importantly, results revealed that the recycled self-healing and multiple stimulus response ability of nanoparticles-modified self-healing polyurethane was implemented grounded on four synergistic effects of photothermal effect of nanoparticles, thermo-reversible Diels-Alder reaction, thermal movement of molecular chains and nanoparticles, and the dissociation and regeneration of hydrogen bonds. This research provided an ideal approach for numerous options for cracks repairing used in construction industry when exposed in harsh environments.

研究领域: 材料科学 · 纳米技术 · 高分子化学 · 工程材料
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MACROMOLECULAR BIOSCIENCE · 2014 ·Vol. 14 ·期 10 ·1429-1436 · IF 3.65

Synthesis of Functionalized Poly(ester carbonate) with Laminin-Derived Peptide for Promoting Neurite Outgrowth of PC12 cells

Dongming Xing,Lie Ma,Changyou Gao

Maleimide-functionalized poly(ester carbonate)s are synthesized by ring-opening copolymerization of furan–maleimide functionalized trimethylene carbonate (FMTMC) with L -lactide and a subsequent retro Diels-Alder reaction. The maleimide groups on poly(ester carbonate)s are amenable to Michael addition with thiol-containing molecules such as 3-mercapto-1-propanol, 2-aminoethanethiol hydrochloride, and mercaptoacetic acid under mild conditions, enabling the formation of biodegradable materials with various functional groups (e.g., hydroxyl, amine, and carboxyl). In particular, the maleimide-functionalized poly(ester carbonate) is clicked with a laminin-derived peptide CQAASIKVAV. In vitro culture of PC12 cells shows that the maleimide-functionalized polymers, especially the CQAASIKVAV-grafted one, could support cell proliferation and neurite outgrowth. The maleimide-functionalized poly(ester carbonate)s provide a versatile platform for diverse functionalization and have comprehensive potential in biomedical engineering.

研究领域: 材料科学 · 生物医学工程 · 高分子化学 · 细胞生物学
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