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EUROPEAN POLYMER JOURNAL · 2021 · IF 4.598

Low-dielectric styrene resins with high mechanical strength and good (re)processability via constructing imine-crosslinked network and introducing small amount of amino molecules

Yan Wang,Yang Xiong,Chengyao Hu,Junxiao Yang,Yawen Huang

Materials used in circuit boards need to be recyclable in order to decrease resource waste and mitigate environmental pollution. However, it is challenging to prepare resins with high mechanical strength while preserving their good reprocessing and low dielectric property. In this study, an adaptable imine crosslinking network (imine-CAN) was constructed and a free amine compound (dodecylamine, DDA) was introduced to obtain styrene resins exhibited good (re)processability even at a high crosslinking density. The resin has a low dielectric constant of 2.71 and high mechanical strength of 52 MPa. Moreover, after reprocessing three times, the dielectric constants of the PS-imines remained constant and 94% mechanical strength was recovered. Further investigation indicated that the (re)processability and decrosslinking at high temperatures were regulated by incorporating different amounts of DDA. PS-imines showed superior mechanical and reprocessing performance compared to most current reprocessable resins. These new vitrimers could be potential candidates for use in recyclable circuit boards.

研究领域: 材料科学 · 环境科学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Dynamic imine crosslinking for waterproof starch plastic with tunable mechanical properties

Guowen Zhou,Xiaoqian Zhang,Zepeng Lei,Haonan Zhou,Xiaohui Wang

Starch-based plastics offer a potential solution to environmental pollution and can reduce the dependence on petroleum-based plastics. However, effectively preparing starch-based plastics with moisture resistance and high strength remains challenging. Herein, dialdehyde starch (DAS) with different degrees of oxidation was first synthesised. The molecular weight and crystallinity of DAS decreased depending on the aldehyde content, as determined through scanning electron microscopy, X-ray diffraction and molecular weight analyses. Subsequently, a sustainable starch plastic (DAS-DA) was prepared via the dynamic imine crosslinking of DAS with diamines. The influence of the degree of oxidation of DAS on the structure and properties of DAS-DA was systematically investigated. No linear relationship was observed between the tensile strength of DAS-DA and the aldehyde content of DAS. When the aldehyde content was 41.1 %, the resulting DAS41-DA exhibited optimal mechanical strength (27.8 MPa), exceeding that of most reported starch-based plastics. In addition, owing to the presence of imine crosslinking networks, DAS41-DA exhibited excellent water and solvent resistance (>60 days), good thermal stability (456 °C–462 °C) and excellent reprocessability and biodegradability. These findings provide a theoretical basis for the preparation of high-performance bioplastics from aldehyde-containing polysaccharides.

CAS / MDL: 646-25-3 7790-28-5
研究领域: 材料科学 · 环境科学 · 高分子化学
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CARBOHYDRATE POLYMERS · 2021 · IF 9.381

Characterization and antibacterial properties of epsilon-poly- l-lysine grafted multi-functional cellulose beads

Chunling Nie,Ting Shen,Weicheng Hu,Qin Ma,Jiahui Zhang,Shuqian Hu,Huafeng Tian,Hao Wu,Xiaogang Luo,Jianguo Wang

In recent years, harmful microorganisms in water pose great harm to ecological environment and human health. To solve this problem, epsilon-poly- l -lysine (EPL) grafted cellulose beads were prepared via 2, 2, 6, 6-tetramethylpiperidine-1-oxyl (TEMPO) mediated oxidation and carbodiimide mediated cross-linking reaction. Hydroxyl groups on C6 of cellulose were oxidized to carboxyl groups by TEMPO and grafting reaction was achieved between newly formed carboxyl groups of cellulose and amino of EPL. The beads were characterized by FTIR, SEM, XRD and TGA. The crystalline form of cellulose transformed from cellulose I to cellulose II after being dissolved and regenerated. The grafted cellulose beads showed good antibacterial activities against Gram-negative Escherichia coli , Gram-positive Staphylococcus aureus and Alicyclobacillus acidoterrestris with 10 h. The beads could be biodegraded in soil after 28 days. It is expected that the bio-based composite beads could have potential applications in water purification and food treatment fields.

研究领域: 材料科学 · 环境科学 · 生物技术 · 化学
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Soft Matter · 2020 ·Vol. 16 ·期 18 ·4540-4548 · IF 3.14

Bioactive scaffolds based on collagen filaments with tunable physico-chemical and biological features

Ting Lu,Hong Hu,Yuanqi Li,Qingsong Jiang,Jinlei Su,Hai Lin,Yun Xiao,Xiangdong Zhu,Xingdong Zhang

Native tissues such as nerve bundles, blood vessels and tendons have extracellular matrices with a characteristic linear orientation, which cannot be fully achieved with the current technology for the development of regenerative biomaterials. In this study, bioactive and oriented collagen filaments have been fabricated using a combination of wet-spinning and carbodiimide-based crosslinking. The wet-spinning techniques, including extrusion and collection rates, and their influences on collagen filaments were studied and optimized. The diameter of the attained collagen filaments can be adjusted ranging from 30 μm to 650 μm. Further characterizations, such as circular dichroism, scanning electron microscopy, small-angle X-ray scattering and Fourier transform infrared spectra analysis, showed that the native structure of the collagen was greatly preserved after the filament preparation process. The measurements of weight swelling ratio and degradation rate indicate that the crosslinking method can efficiently regulate the physico-chemical properties of collagen filaments, including water absorption and degradation behaviors. In particular, the mechanical strength of collagen filaments can be greatly improved via crosslinking. In addition, cells can adhere and spread on collagen filaments in well-aligned patterns, showing appropriate biological features. It can be concluded that the bioactive collagen filaments with tunable properties are preferable for developing tissue engineering scaffolds with characteristic orientation features. With further study of the interactions between collagen filaments and cells, this work may shed light on the development of collagen based biomaterials that would be beneficial in the field of tissue engineering.

CAS / MDL: 25952-53-8 6066-82-6
研究领域: 生物材料 · 组织工程 · 生物医学工程
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JOURNAL OF MATERIALS SCIENCE · 2024 ·Vol. 59 ·期 9 ·4059-4071 · IF 3.5

Vanillin-based degradable thermosets with superior dielectric properties via regulation of imine cross-linked structure

Lyu Maoping,Liu Yingchun,Cui Xiaohua,Liang Liyan

Developing cross-linked polymers with both low dielectric constant and degradability for microelectronics and sustainability remains a challenge. Herein, a new fluoro-containing dialdehyde monomer (VF) derived from vanillin was synthesized, which was then cross-linked with a tris (2-aminoethyl) amine (TREN) and different diamines (4, 4 ′ -methylenebis (cyclohexylamine) (PACM), 4, 4 ′ -diaminodiphenylmethane (DDM) and 1, 6-hexamethylenediamine (HMDA)) to give three polyimines thermosets, namely VFT-P, VFT-D and VTF-H, respectively, showing controlled comprehensive properties through regulation of imine cross-linked structures. Properties-function relationship of these polyimines was systematically studied and focused mainly on revealing the degradation process and the mechanism of the degradability of polyimines. The results indicated that among these polyimines, VFT-P exhibited superior conventional properties and acid resistance due to its appropriate reactivity, cross-linked density, rigid non-conjugated Schiff base structures, and high free volume. The storage modulus, glass transition temperature, transmittance, and tensile strength of VFT-P polyimines could reach 3.40 GPa, 134 °C,  > 97% (at 500–800 nm) and 62.47 ± 3.65 MPa, respectively. Besides, a low dielectric constant of 2.96 at 100 MHz and superior degradability was achieved. This study introduces a facile and effective design strategy to achieve the compatibility of target properties and also offers a potentially sustainable alternative to conventional cross-linked dielectric polymers. Graphical abstract

研究领域: 高分子科学 · 材料工程 · 微电子学 · 有机合成 · 介电材料 · 可持续化学
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Biomedical Materials · 2021 ·Vol. 16 ·期 4 ·045022 · IF 3.715

A novel detergent-based decellularization combined with carbodiimide crosslinking for improving anti-calcification of bioprosthetic heart valve

Yu Luo,Shenyu Huang,Lie Ma

Currently, valve replacement surgery is the only therapy for the end-stage valvular diseases because of the inability of regeneration for diseased heart valves. Bioprosthetic heart valves (BHVs), which are mainly derived from glutaraldehyde (GA) crosslinked porcine aortic heart valves or bovine pericardium, have been widely used in the last decades. However, it is inevitable that calcification and deterioration may occur within 10–15 years, which are still the main challenges for the BHVs in clinic. In this study, N-Lauroylsarcosine sodium salt (SLS) combined with N-(3-Dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) were utilized to decellularize and crosslink the heart valves instead of GA treatment. The obtained BHVs exhibited excellent extracellular matrix stability and mechanical properties, which were similar with GA treatment. Moreover, the obtained BHVs exhibited better in vitro biocompatibilities than GA treatment. After subcutaneous implantation for 30 d, the obtained BHVs showed mitigated immune response and reduced calcification compare with GA treatment. Therefore, all the above results indicated that the treatment of SLS-based decellularization combined with EDC/NHS crosslink should be a promising method to fabricate BHVs which can be used in clinic in future.

研究领域: 心血管工程 · 组织工程 · 生物医学材料
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POLYMERS FOR ADVANCED TECHNOLOGIES · 2025 ·Vol. 36 ·期 8 ·e70303 · IF 3.4

Stepwise Surface Engineering of Sr10-HA-g-PBLG Porous Microspheres: Precise Functionalization for In Situ Scaffold Formation via Dynamic Crosslinking

Shenghua Xu,Weihong Guo

This study develops a sequential surface functionalization strategy for strontium-substituted hydroxyapatite-graft-poly(γ-benzyl-L-glutamate) (Sr10-HA- g -PBLG) porous microspheres to enable in situ scaffold assembly. Hydrazine hydrate-mediated aminolysis and alkaline hydrolysis introduced surface amino (2.87 × 10 −2 mol/g) and carboxyl (1.76 × 10 −2 mol/g) groups, respectively, while preserving structural integrity (verified by FT-IR/XRD/SEM). Subsequent EDC/NHS-activated grafting of 3-amino-1,2-propanediol (AP) achieved 90% efficiency, followed by NaIO 4 oxidation to generate aldehyde functionalities (2.65 × 10 −3 mol/g). Through dynamic imine crosslinking between aldehyde- and amino-functionalized microspheres, 3D scaffolds were formed in situ. The scaffolds exhibited hierarchical porosity (pore size: 40–60 μm, porosity: 85.4% ± 2.3%), exceptional hydration capacity (613.6% ± 24.1% water retention), and enhanced mechanical properties (storage modulus > 13,000 Pa, compressive strength: 0.53 ± 0.02 MPa, tensile strength: 0.068 ± 0.02 MPa). Controlled degradation in PBS (pH = 7.4) showed 46.24% mass loss over 31 weeks. This interfacial engineering approach provides a versatile platform for designing polymer-ceramic hybrids with tailorable surface reactivity and structural adaptability. Adipose-derived stem cells were cultured in vitro, and the dual-fluorescence tracking strategy revealed spatially coordinated cellular colonization patterns, demonstrating porous microsphere scaffold's potential for precision-controlled 3D cell delivery in tissue engineering applications.

CAS / MDL: 129-00-0 81-88-9 92-31-9
研究领域: 材料科学 · 生物医学工程 · 组织工程 · 高分子化学 · 陶瓷工程 · 表面工程 · 纳米技术
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Acta Biomaterialia · 2022 · IF 10.633

Microfluidic-templated cell-laden microgels fabricated using phototriggered imine-crosslinking as injectable and adaptable granular gels for bone regeneration

Chuanfeng An,Renjie Zhou,Haoyue Zhang,Yujie Zhang,Weijian Liu,Jia Liu,Bingkun Bao,Kai Sun,Changle Ren,Yang Zhang,Qiuning Lin,Lijun Zhang,Fang Cheng,Jiankang Song,Linyong Zhu,Huanan Wang

Injectable granular gels consisting of densely packed microgels serving as scaffolding biomaterial have recently shown great potential for applications in tissue regeneration , which allow administration via minimally invasive surgery, on-target cargo delivery, and high efficiency in nutrient/waste exchange. However, limitations such as insufficient mechanical strength , structural integrity, and uncontrollable differentiation of the encapsulated cells in the scaffolds hamper their further applications in the biomedical field. Herein, we developed a new class of granular gels via bottom-up assembly of cell-laden microgels via photo-triggered imine-crosslinking (PIC) chemistry based on the microfluidic technique. The particulate nature of the granular gels rendered them with shear-thinning and self-healing behavior, thereby functioning as an injectable and adaptable cellularized scaffold for bone tissue regeneration. Specifically, single cell-laden, monodisperse microgels composed of methacrylate- and o-nitrobenzene-functionalized hyaluronic acid and gelatin were prepared using a high-throughput microfluidic technique with a production rate up to 3.7 × 10 8 microgels/hr, wherein the PIC chemistry alleviated the oxygen inhibition on free-radical polymerization and facilitated enhanced fabrication accuracy, accelerated gelation rate, and improved network strength. Further in vitro and in vivo studies demonstrated that the microgels can serve as carriers to support the activity of the encapsulated mesenchymal stem cells; these cell-laden microgels can also be used as cellularized bone fillers to induce the regeneration of bone tissues as evidenced by the in vivo experiment using the rat femoral condyle defect model. In general, these results represent a significant step toward the precise fabrication of engineered tissue mimics with single-cell resolution and high cell-density and can potentially offer a powerful tool for the design and applications of a next generation of tissue engineering strategy. Statement of significance Using microfluidic droplet-based technology, we hereby developed a new class of injectable and moldable granular gels via bottom-up assembly of cell-laden microgels as a versatile platform for tissue regeneration. Phototriggered imine-crosslinking chemistry was introduced for microgel cross-linkage, which allowed for the fabrication of microgels with improved matrix homogeneity, accelerated gelation process, and enhanced mechanical strength. We demonstrated that the microgel building blocks within the granular gels facilitated the proliferation and differentiation of the encapsulated mesenchymal stem cells, which can further serve as a cellularized scaffold for the treatment of bone defects.

CAS / MDL: 647-42-7 678-39-7
研究领域: 组织工程 · 生物材料 · 生物医学工程 · 再生医学
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