European Polymer Journal最新文献_第2页

Biobased and biodegradable polyester amides based on nylon 6,6 and polybutylene adipate via straightforward bulk polymerization

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-22 DOI: 10.1016/j.eurpolymj.2024.113594

Cornelis Post , Jeroen van der Vlist , Jesse A. Jongstra , Rudy Folkersma , Vincent S.D. Voet , Katja Loos

Aliphatic polyesters are generally known for their limited thermal and mechanical properties, but are prone to biodegradation. On the other hand, aliphatic polyamides, mainly represented by nylons, feature high thermal transition points and enhanced mechanical strength, but are usually classified as nonbiodegradable. In this work, the properties of the aliphatic polyester polybutylene adipate and nylon 6,6 were combined by synthesizing polyester amides. Relatively low- and high-molecular weight series,

\bar{M_{n}}

7000 and 14400 g/mol, respectively, were synthesized via a straightforward bulk polymerization process by utilizing biobased starting materials: butanediol, adipic acid and nylon 6,6 salt. The amide-to-ester ratio was varied to analyze the influence of the amide content on the molecular structure, thermal properties, mechanical properties, hydrophilicity and biodegradability. Strong relationships between the amide content and the T_g, T_m, degree of crystallinity, and mechanical properties were observed. Water contact angle measurements revealed that all the polyester amides were hydrophilic. Finally, the biodegradation experiments demonstrated that all polyester amides are prone to biodegradation in activated sludge and that the amide content had a major influence on the biodegradation rate. This work supports the high potential of biobased polyester amides for applications in numerous fields due to their versatility in terms of polymeric properties and sustainable character.

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引用次数: 0

Strong and conductive gelatin hydrogels enhanced by Hofmeister effect and genipin crosslinking for sensing applications 通过霍夫迈斯特效应和基因素交联增强的强导电明胶水凝胶用于传感应用

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-21 DOI: 10.1016/j.eurpolymj.2024.113583

Jie Liu , Zhilu Rao , Yitong Dong , Xuejing Zheng , Keyong Tang

There is a growing interest in the development of conductive hydrogels based on natural polymers for sensing applications due to their flexibility, versatility and environmental friendliness. However, achieving strong hydrogels capable of withstanding mechanical stress while maintaining their desirable characteristics remains a challenge. This study proposed a strategy to tailor the mechanical and electrical conductivity of gelatin hydrogels by combining genipin crosslinking with the modulation of aggregation states of gelatin chains through Hofmeister effect. The obtained conductive gelatin hydrogels exhibit high tensile strength (5.48 MPa) and compressive stress at 80 % strain (5.66 MPa), excellent stretchability (>500 %), remarkable freezing-resistant performance, and good strain sensitivity. By virtue of these outstanding properties, the hydrogels were used as strain sensors for human motion detection, demonstrating a gauge factor of 0.6 at 110–200 % tensile strain. Additionally, the hydrogel sensors demonstrate a rapid response time (<0.32 s) and can withstand cyclic tensile/compressive loads at both room temperature and −20 °C, owing to their compact and stable network structure formed by the synergistic action of Hofmeister effect and chemical crosslinking. The strain sensors based on gelatin hydrogels can detect and track human movements, indicating promising applications in the field of wearable technology.

由于天然聚合物具有灵活性、多功能性和环境友好性，人们对开发用于传感应用的导电水凝胶越来越感兴趣。然而，如何实现既能承受机械应力又能保持理想特性的强力水凝胶仍然是一项挑战。本研究提出了一种策略，即通过霍夫迈斯特效应将基因素交联与明胶链的聚集状态调节相结合，从而定制明胶水凝胶的机械和导电性。所获得的导电明胶水凝胶具有较高的拉伸强度（5.48 兆帕）和 80% 应变时的压缩应力（5.66 兆帕）、优异的拉伸性（500%）、显著的抗冻性能和良好的应变敏感性。凭借这些出色的性能，这种水凝胶被用作人体运动检测的应变传感器，在拉伸应变为 110%-200% 时的测量系数为 0.6。此外，由于水凝胶在霍夫迈斯特效应和化学交联的协同作用下形成了紧凑稳定的网络结构，因此水凝胶传感器的响应速度很快（0.32 秒），并能在室温和零下 20 ℃ 的环境中承受循环拉伸/压缩载荷。基于明胶水凝胶的应变传感器可以检测和跟踪人体运动，这表明其在可穿戴技术领域的应用前景广阔。

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引用次数: 0

4D printing of pH-responsive bilayer with programmable shape-shifting behaviour

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-19 DOI: 10.1016/j.eurpolymj.2024.113581

Smruti Parimita , Amit Kumar , Hariharan Krishnaswamy , Pijush Ghosh

4D printing of smart materials has seen remarkable advancements in the domain of biomedical devices, with a particular focus on developing responsive and adaptive programmable structures. In this work, we report the 4D printing of two solvent-responsive hydrogels forming a bilayer that undergoes bidirectional actuation depending on the pH of the solvent. A strong interlayer adhesion between the hydrogels is formed without subjecting either of their surfaces to any chemical modification. These hydrogels have an interfacial toughness of 71.8 J/m² and undergoes no delamination during actuation inside a solvent. Conventionally, pH-responsive actuators are only limited to simple 2D films prepared by solvent casting. However, our work focuses on the design and fabrication of complex bilayer and patterned structures using Direct-Ink Writing (DIW) approach. These printed structures actuate upon immersion in a solvent medium, and the actuation is reversible in nature. The influence of programmable variables on the morphed structure was studied systematically by modifying the rheological properties (in the range of

1 0^{2}

–

1 0^{5}

Pa s) and printing parameters (optimized at a printing speed of 5 mm/sec, with the extrusion pressure of 5–6 bar and nozzle diameter of 0.5 mm) of the 3D printed bilayer structure. The physicochemical properties of the printable hydrogel ink were tuned such that the same structure can respond to both acidic and basic pH (with non-morphing point at pH 7), by altering the directionality of actuation. We have demonstrated the applications of these pH-responsive actuators in smart valves.

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引用次数: 0

Spontaneous gradient copolymers of N-vinylsuccinimide/N-vinylsuccinamic acid with O-cholesteryl (meth)acrylate via RAFT polymerization as potential drug delivery systems 通过 RAFT 聚合将 N-乙烯基琥珀酰亚胺/N-乙烯基琥珀酸与 O-胆固醇（甲基）丙烯酸酯自发梯度共聚物用作潜在的药物输送系统

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-17 DOI: 10.1016/j.eurpolymj.2024.113586

Mariia L. Levit , Evgenii V. Sivtsov , Ekaterina S. Sinitsyna , Irina O. Bagaeva , Anatolii V. Dobrodumov , Alexandra L. Nikolaeva , Natalia V. Zakharova , Alexey I. Gostev , Sergey A. Silonov , Iosif V. Gofman , Evgenia G. Korzhikova-Vlakh

Today, biocompatible and bioinspired well-defined copolymers with the ability to form nanoparticles are of great interest as potential drug delivery systems. In this study, we report the synthesis of novel biocompatible copolymers from monomers with different activity and capable of forming gradient copolymers by RAFT polymerization. In particular, the copolymerization of N-vinylsuccinimide (VSI) and O-cholesteryl (meth)acrylate (Ch(M)A) mediated by S,S’-dibenzyl trithiocarbonate (DBTTC) has been thoroughly studied by varying the monomer ratio and the ratio of monomer to RAFT agent. Important dependencies such as molecular weight and monomer conversion versus time, and molar fraction of monomer units as a function of monomer conversion were investigated. The obtained copolymers were thoroughly characterized using a number of physicochemical methods such as ¹H NMR, ¹H–¹³C HSQC and ATR-IR-spectroscopy, size-exclusion chromatography, static and dynamic light-scattering, as well as thermogravimetric analysis. In addition, the reactivity ratios of VSI and ChMA were determined and the dyad and triad compositions of the copolymers were calculated from the obtained values. The synthesized P(VSI-co-Ch(M)A) were subjected to selective hydrolysis of succinimide ring to convert it into succinamic acid. This approach yields a set of bioinspired amphiphilic copolymers based on N-vinylsuccinamic acid (VSAA) and Ch(M)A. The synthesized series of P(VSI-co-Ch(M)A) and P(VSAA-co-Ch(M)A) were used to obtain nanoparticles by nanoprecipitation or self-assembly via direct dissolution in aqueous medium. In addition, the method of surface hydrolysis of VSI units in pre-formed P(VSI-co-Ch(M)A) nanoparticles was applied to produce nanoparticles with hydrophilic negatively charged surface and enhanced stability. All techniques were optimized to prepare nanoparticles with characteristics suitable for systems considered for drug delivery. Successful loading of the antitumor drug irinotecan into nanoparticles was achieved with high encapsulation efficacies. The storage stability of empty and irinotecan loaded nanoparticles were studied in various media (water, saline solution, serum containing cell culture medium) under room and refrigerator conditions. The developed empty nanoparticles exhibited low rate of uptake by macrophages and low cytotoxicity to irinotecan-sensitive colon cancer cells (Caco-2). In turn, the irinotecan-loaded nanoparticles demonstrated inhibitory activity against Caco-2 cells comparable to the free drug.

如今，具有生物相容性和生物启发的、可形成纳米颗粒的定义明确的共聚物作为潜在的药物输送系统备受关注。在本研究中，我们报告了利用具有不同活性的单体通过 RAFT 聚合反应合成新型生物相容性共聚物的情况，这些单体能够形成梯度共聚物。通过改变单体比例和单体与 RAFT 剂的比例，我们对 S,S'-二苄基三硫代碳酸酯（DBTTC）介导的 N-乙烯基琥珀酰亚胺（VSI）和 O-胆固醇基（甲基）丙烯酸酯（Ch(M)A）的共聚进行了深入研究。研究了分子量和单体转化率与时间的关系，以及单体单元的摩尔分数与单体转化率的关系等重要的相关性。采用多种物理化学方法，如 1H NMR、1H-13C HSQC 和 ATR-IR-光谱法、尺寸排阻色谱法、静态和动态光散射法以及热重分析法，对所获得的共聚物进行了全面的表征。此外，还测定了 VSI 和 ChMA 的反应活性比，并根据所得数值计算了共聚物的二元和三元组成。对合成的 P(VSI-co-Ch(M)A)进行琥珀酰亚胺环选择性水解，将其转化为琥珀酸。这种方法产生了一组基于 N-乙烯基琥珀酸（VSAA）和 Ch(M)A 的生物启发两亲共聚物。合成的 P(VSI-co-Ch(M)A)和 P(VSAA-co-Ch(M)A)系列共聚物可通过纳米沉淀或在水介质中直接溶解自组装获得纳米颗粒。此外，还采用了对预形成的 P（VSI-co-Ch（M）A）纳米粒子中的 VSI 单元进行表面水解的方法，制备出表面亲水性负电荷且稳定性更强的纳米粒子。对所有技术进行了优化，以制备出具有适合药物输送系统特性的纳米颗粒。成功地将抗肿瘤药物伊立替康装入纳米颗粒，并实现了高封装效率。研究了空纳米颗粒和伊立替康负载纳米颗粒在不同介质（水、生理盐水、含血清的细胞培养基）中，在室温和冰箱条件下的储存稳定性。所开发的空纳米粒子的巨噬细胞吸收率低，对伊立替康敏感的结肠癌细胞（Caco-2）的细胞毒性低。反过来，负载伊立替康的纳米颗粒对 Caco-2 细胞的抑制活性与游离药物相当。

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引用次数: 0

Mechanically strong, reprocessable and chemically recyclable furan-based poly(acylhydrazone)s materials with hydrogen-bonding networks 具有氢键网络的机械强度高、可再加工和化学可回收的呋喃基聚（酰基腙）材料

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-15 DOI: 10.1016/j.eurpolymj.2024.113584

Xiaowei Li , Chilong Liu , Xiaoru Quan, Yanxin Zhang, Su Wang, Shuangfei Zhao, Jiming Yang, Yirong Feng, Wei He, Kai Guo

Acylhydrazone linkages are attractive in designing reconfigurable and chemically recyclable polymer due to their reversible characteristics and ease of preparation. We fabricate mechanically strong, thermally stable and chemically recyclable poly(acylhydrazone)s (pDFF-IPDH) using biobased 2,5-diformylfuran (DFF) and dihydrazide compounds as monomers. The linear chains are physically cross-linked via hydrogen bonding between the acylhydrazone moieties. The pDFF-IPDH sample exhibits good mechanical properties, offering both high strength and toughness. The linear and reversible acylhydrazone backbones endow polymers with attractive temperature-dependent dynamic natures, which enables the topological network to rearrange, giving the poly(acylhydrazone)s excellent reprocessability. Moreover, the feasibility of formaldehyde-promoted depolymerization presents an effective recycling pathway, offering promising opportunities in addressing the challenge between recyclability and service performance.

酰基腙连接因其可逆特性和易于制备而在设计可重构和化学可回收聚合物方面具有吸引力。我们以生物基 2,5-二甲酰基呋喃（DFF）和二酰肼化合物为单体，制备出机械强度高、热稳定性好且可化学回收的聚酰腙（pDFF-IPDH）。线性链通过酰腙分子之间的氢键进行物理交联。pDFF-IPDH 样品具有良好的机械性能，同时具有高强度和韧性。线性和可逆的酰基腙骨架赋予聚合物极具吸引力的温度动态特性，使拓扑网络能够重新排列，从而赋予聚（酰基腙）极佳的再加工性。此外，甲醛促进解聚的可行性提供了一种有效的回收途径，为解决可回收性和使用性能之间的难题提供了大有可为的机会。

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引用次数: 0

Progress in synthesis and applications of Polyaniline-Coated Nanocomposites: A comprehensive review 聚苯胺涂层纳米复合材料的合成与应用进展：综述

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-15 DOI: 10.1016/j.eurpolymj.2024.113574

Priya Kaushik , Ruchi Bharti , Renu Sharma , Monika Verma , Richard T. Olsson , Annu Pandey

This review explores the synthesis, characterization, and diverse applications of polyaniline (PANI)-based nanocomposites. PANI, known for its tunable electrical conductivity, eco-stability, and cost-effectiveness, has gained significant attention in advanced materials. This study focused on various preparation techniques, such as chemical oxidative polymerization, electrochemical polymerization, and vapor phase polymerization, highlighting their unique characteristics and impacts on nanocomposite performance. Critical applications of PANI nanocomposites are examined, including their roles in supercapacitors, sensors, solar cells, anticorrosion devices, water purification, and catalysis. Integrating PANI with metals, metal oxides, graphene, and carbon nanostructures enhances its functionality, making it a versatile candidate for innovative technological solutions. This review also addresses the challenges in commercializing PANI nanocomposites and proposes future research directions to overcome these obstacles.

本综述探讨了基于聚苯胺（PANI）的纳米复合材料的合成、表征和各种应用。PANI 因其可调的导电性、生态稳定性和成本效益而闻名，在先进材料领域备受关注。本研究重点研究了各种制备技术，如化学氧化聚合、电化学聚合和气相聚合，突出了它们的独特性及其对纳米复合材料性能的影响。研究还探讨了 PANI 纳米复合材料的关键应用，包括其在超级电容器、传感器、太阳能电池、防腐设备、水净化和催化作用中的作用。将 PANI 与金属、金属氧化物、石墨烯和碳纳米结构结合可增强其功能，使其成为创新技术解决方案的多功能候选材料。本综述还探讨了 PANI 纳米复合材料商业化所面临的挑战，并提出了克服这些障碍的未来研究方向。

引用次数: 0

Development of organosoluble, quaternized and naproxen sodium- loaded poly(vinyl alcohol)-based electrospun nanofibers 开发有机可溶、季铵化和负载萘普生钠的聚乙烯醇基电纺纳米纤维

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-14 DOI: 10.1016/j.eurpolymj.2024.113565

Gokhan Acik , Neslihan Turhan Cakir , Cagatay Altinkok

Electrospinning is an effective and common method utilized to produce fibers from sub-micrometer to nanoscale. Although poly(vinyl alcohol) (PVA) can be easily electrospun in water, its widespread usage limited in electrospinning applications due to its poor solubility in organic solvents. In this regard, this study concentrated on partially modifying of PVA via chemical transformation by treating with dichloroacetic acid (DCAA) (poly(VA-co-VDCAc)) and triethyl amine (TEA) (poly(VA-co-VDCAc-co-QVAc)), respectively to increase organosolubility as well as provide antibacterial activity. Additionally, the modal drug, namely naproxen sodium (NAP), was incorporated into the modified polymer matrixes by simple blending. Electrospinning method was applied to fabricate the organosoluble, quaternized and NAP-loaded PVA-based nanofibers as potential drug carriers in controlled drug release. The chemical structure, morphology, wettability as well as the thermal features of the obtained nanofibers and their precursors at various stages were investigated using Fourier-transform infrared (FT-IR), proton nuclear magnetic resonance (¹H NMR) spectroscopies, scanning electron microscopy (SEM), water contact angle (WCA) measurements, thermogravimetric and differential scanning calorimetry (TGA and DSC) analyses, respectively. SEM images proved that the nanofibers had noticeably smooth, cylindrical, uniform, and continuous and the modification reactions were affected the mean diameter of the samples. The utilization of modified electrospun PVA-based nanofibers as carrier for delivery of naproxen sodium (NAP) was elucidated. Release behaviors of the electrospun fibers were determined at pH 7.4, and the release of the NAP was faster for non-quaternized sample. Antibacterial activity of electrospun nanofibers against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) bacteria was evaluated in vitro, and poly(VA-co-VDCAc-co-QVAc)s electrospun nanofibers have better potential in killing bacteria. Overall, this research provides useful guidance for tailoring electrospinning processes for drug delivery of PVA-based materials.

电纺丝是生产亚微米级到纳米级纤维的一种有效而常用的方法。虽然聚乙烯醇（PVA）可以在水中轻松电纺，但由于其在有机溶剂中的溶解性较差，其在电纺应用中的广泛使用受到了限制。为此，本研究主要通过化学转化对 PVA 进行部分改性，分别用二氯乙酸（DCAA）（poly(VA-co-VDCAc)）和三乙胺（TEA）（poly(VA-co-VDCAc-co-QVAc)）处理，以增加有机溶解性并提供抗菌活性。此外，还通过简单的混合将萘普生钠（NAP）这种模式药物加入到改性聚合物基质中。应用电纺丝方法制备了有机溶解、季铵化和负载 NAP 的 PVA 基纳米纤维，作为潜在的药物载体用于药物控释。利用傅立叶变换红外光谱（FT-IR）、质子核磁共振（1H NMR）光谱、扫描电子显微镜（SEM）、水接触角（WCA）测量、热重分析和差示扫描量热法（TGA 和 DSC）分析，分别研究了所制备纳米纤维及其前体在不同阶段的化学结构、形态、润湿性和热学特征。扫描电镜图像表明，纳米纤维具有明显的光滑性、圆柱形、均匀性和连续性，改性反应影响了样品的平均直径。研究阐明了改性电纺 PVA 基纳米纤维作为载体给药萘普生钠（NAP）的应用。测定了电纺纤维在 pH 值为 7.4 时的释放行为，结果表明非季铵化样的萘普生钠释放速度更快。体外评估了电纺纳米纤维对大肠杆菌和金黄色葡萄球菌的抗菌活性，结果表明聚（VA-co-VDCAc-co-QVAc）电纺纳米纤维具有更好的杀菌潜力。总之，这项研究为定制 PVA 基材料的药物递送电纺工艺提供了有益的指导。

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引用次数: 0

Versatile organosilicone porous materials for the detection of nitroaromatics and the visualization of fingerprints 多用途有机硅多孔材料，用于检测硝基芳香族化合物和可视化指纹

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-14 DOI: 10.1016/j.eurpolymj.2024.113576

Yafang Zhang , Pengfei Hua , Yanfu Chai , Yujing Zuo

Achieving explosive detection and fingerprints visualization at the same time is of great significance. Towards this end, based on the cage structure and multiple reaction sites of octavinyl polyhedral oligomeric silsesquioxane (OVS), a series of multifunctional silicone porous materials OVSBs and OVSTs were designed and synthesized with 1,3,5-triphenylbenzene and 2,4,6-triphenyl-1,3,5-triazine. These porous materials have narrow pore size distribution, high specific surface area and pony-sized that smaller than 5 nm. The micropore volume ratio of porous materials can be changed by regulating the molar ratio of OVS to functional compounds. OVSB-2 shows excellent adsorption capacity for fluorescent dyes due to its highest specific surface area and high micropore volume ratio. OVSB-2 also has superior fluorescence characteristic, which can quickly detect nitroaromatic compounds within 20 s. This work provided a new method for expanding the application of silicone mesoporous materials in explosive detection and fingerprints visualization simultaneously.

同时实现爆炸物检测和指纹可视化具有重要意义。为此，基于八乙烯基多面体低聚硅倍半氧烷（OVS）的笼状结构和多反应位点，设计并用 1,3,5-三苯基苯和 2,4,6-三苯基-1,3,5-三嗪合成了一系列多功能有机硅多孔材料 OVSBs 和 OVSTs。这些多孔材料的孔径分布窄，比表面积高，孔径小于 5 纳米。通过调节 OVS 与功能化合物的摩尔比，可以改变多孔材料的微孔体积比。OVSB-2 具有最大的比表面积和较高的微孔体积比，因此对荧光染料具有出色的吸附能力。这项工作为扩大有机硅介孔材料在爆炸物检测和指纹可视化方面的应用提供了一种新方法。

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引用次数: 0

Preparation of free radical/cationic hybrid UV-cured silicone materials with reducing oxygen inhibition via silyl radicals 制备通过硅基抑制还原氧的自由基/阳离子混合紫外线固化硅材料

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-14 DOI: 10.1016/j.eurpolymj.2024.113582

Xiaoquan Li , Fuping Bian , Rui Huang , Jiyan Wei , Xuefeng Gui , Jiwen Hu , Shudong Lin

UV-curing technology is a new, green technology with the advantages of being efficient, energy-saving, and environmentally friendly; however, there is a general oxygen-inhibition problem during the UV-curing process, especially when silicone acrylates are applied to the UV-curing treatment. Herein, epoxy-based silicone prepolymers (ESP) containing Si-H bonds were prepared through the hydrosilylation reaction of poly(dimethylsiloxane-co-methylhydrosiloxane) (PDMS-PHMS) and allyl glycidyl ether (AGE) to graft epoxy groups onto silicone segments while retaining part of the Si-H bond. The epoxy groups in the prepolymers are capable of cationic photopolymerization, and the retained Si-H bonds in the prepolymers can generate highly reactive silyl radicals for initiating free-radical photopolymerization. The anti-oxygen inhibition ability of silicone acrylates was enhanced with the addition of ESPs. Through experimental investigation, it was found that ESP-3 grafted with 0.30% epoxy groups had the best effect on reducing oxygen inhibition, and the silicone acrylates were able to undergo UV curing in air without sticky surfaces when the added amounts of ESP-3 were at 20 wt%. The addition of ESP-3 has no major impact on the transparency and thermal performance of the UV-cured coatings and further enhances their hydrophobic properties. The free radical/cationic hybrid UV-cured silicone materials reduce the problem of oxygen inhibition, and the UV-cured silicone materials have great potential as hydrophobic and self-cleaning materials.

紫外固化技术是一种新型绿色技术，具有高效、节能、环保等优点，但在紫外固化过程中普遍存在氧抑制问题，尤其是在应用硅丙烯酸酯进行紫外固化处理时。本文通过聚（二甲基硅氧烷-共甲基氢硅氧烷）（PDMS-PHMS）和烯丙基缩水甘油醚（AGE）的氢硅烷化反应，将环氧基团接枝到有机硅片段上，同时保留部分 Si-H 键，从而制备出含有 Si-H 键的环氧基有机硅预聚合物（ESP）。预聚物中的环氧基团可进行阳离子光聚合，而预聚物中保留的 Si-H 键可产生高活性硅基自由基，从而引发自由基光聚合反应。添加静电除尘器后，有机硅丙烯酸酯的抗氧抑制能力得到增强。通过实验研究发现，接枝了 0.30% 环氧基团的 ESP-3 对减少氧抑制的效果最好，当 ESP-3 的添加量为 20 wt% 时，有机硅丙烯酸酯能够在空气中进行紫外固化，且不会出现表面发粘的现象。添加 ESP-3 对紫外线固化涂层的透明度和热性能没有重大影响，并能进一步增强其疏水性能。自由基/阳离子混合紫外固化有机硅材料减少了氧抑制问题，紫外固化有机硅材料作为疏水和自清洁材料具有很大的潜力。

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引用次数: 0

3D bioprinting of thick core–shell vascularized scaffolds for potential tissue engineering applications 厚核壳血管化支架的三维生物打印技术在组织工程中的潜在应用

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-14 DOI: 10.1016/j.eurpolymj.2024.113564

Zineb Ajji , Arman Jafari , Ali Mousavi , Abdellah Ajji , Marie-Claude Heuzey , Houman Savoji

The promise of tissue engineering in developing functional, living, 3D thick structures has been limited due to the constraints of nutrient and oxygen delivery through diffusion. Although advancements in additive manufacturing approaches have enhanced the fidelity and complexity of 3D (bio)printed constructs, the vascularization of such scaffolds is less investigated. Here, we have leveraged extrusion-based 3D bioprnting of core/shell constructs to develop millimeter-thick scaffolds with embedded microvasculature for potential soft tissue repair. Composites of methacrylated gelatin (GelMA) and gelatin have been used for this purpose. A systematic approach was used to investigate the effect of parameters, such as material and photoinitiator concentrations, and photocuring time, on the properties of constructs. Results have shown the structures have Young’s modulus close to the soft tissues. 3D bioprinting parameters were optimized so that the printing and photo crosslinking procedures did not negatively affect the cell viability. It was also observed that a continuous hollow inner core could be successfully printed within the scaffolds, which upon incorporation of endothelial cells during the 3D bioprinting process, could form micro-vessels embedded in the constructs. Together, our results demonstrate the significant potential of the proposed approach for developing thick vascularized tissue-engineered scaffolds suitable for soft tissue engineering.

由于通过扩散输送营养和氧气的限制，组织工程在开发功能性、活体三维厚结构方面的前景一直很有限。虽然增材制造方法的进步提高了三维（生物）打印结构的保真度和复杂性，但对此类支架的血管化研究较少。在这里，我们利用基于挤压技术的三维生物芯/壳结构，开发出了具有嵌入式微血管的毫米厚支架，用于潜在的软组织修复。为此，我们使用了甲基丙烯酸明胶（GelMA）和明胶的复合材料。该研究采用了一种系统方法来研究材料、光引发剂浓度和光固化时间等参数对构建物特性的影响。结果表明，这些结构的杨氏模量接近软组织。对三维生物打印参数进行了优化，使打印和光交联过程不会对细胞活力产生负面影响。我们还观察到，支架内可以成功打印出连续的中空内核，在三维生物打印过程中加入内皮细胞后，可形成嵌入构建物的微血管。总之，我们的研究结果表明，所提出的方法在开发适用于软组织工程的厚血管组织工程支架方面具有巨大潜力。

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引用次数: 0