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A novel bio-based polybenzoxazine prepared from fluorinated Schiff base and furfurylamine with superior thermal, flame-retardant and superhigh-frequency low dielectric properties 一种由氟化希夫碱和糠胺合成的新型生物基聚苯并恶嗪,具有优异的耐热、阻燃和超高频低介电性能
IF 5.1 3区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2026-01-18 DOI: 10.1016/j.reactfunctpolym.2026.106654
Zijian Feng , Runyang Xiang , Jie Huang , Ming Zeng
In pursuit of high-performance and environmentally friendly materials for superhigh-frequency communication applications, a novel biobased benzoxazine resin (poly(SF-f)) is firstly synthesized from fluorinated Schiff base based bisphenol (SF) and furfurylamine. The bulky fluorinated Schiff base structure in SF can impart low polarity, enhance flame retardancy, and reduce the density of polar group, while low polar and reactive furan ring in furfurylamine can increase the cross-linking density. Interestingly, the newly developed benzoxazine SF-f exhibits the lowest onset polymerization temperature, relatively high exothermic enthalpy, and relatively low activation energy compared to other similar structures, due to the presence of both Schiff base moiety and furan ring. Notably, the prepared benzoxazine resin displays good thermal and flame retardancy properties, including the glass transition temperature of 302 °C, the char yield at 800 °C of 56.5%, the limiting oxygen index of 40.10, the heat release capacity of 30.9 J/g K, the total heat release of 2.9 KJ/g, and UL-94 V-0 rating. Besides, the poly(SF-f) also shows low dielectric constants (2.73, 5 GHz; 2.68, 10 GHz) and low dielectric losses (0.0064, 5 GHz; 0.0062, 10 GHz), resulting from the increased cross-linking density, strengthened hydrogen-bonding, and decreased molecular polarity. Therefore, this study not only provides an effective method to design and prepare bio-benzoxazine resin containing Schiff base with good comprehensive properties of high thermally stable, intrinsic flame-retardant, and superhigh-frequency low dielectric properties, but also gives a new insight for the development of high-performance benzoxazine chemistry.
为了追求超高频通信应用的高性能和环保材料,首次以氟化希夫碱双酚(SF)和糠胺为原料合成了一种新型生物基苯并恶嗪树脂(聚(SF-f))。SF中粗大的氟化席夫碱结构可以赋予低极性,增强阻燃性,降低极性基密度,而糠胺中低极性和活性呋喃环可以增加交联密度。有趣的是,与其他类似结构相比,新开发的苯并杂嗪SF-f具有最低的聚合起始温度、较高的放热焓和较低的活化能,这是由于希夫碱部分和呋喃环的存在。值得注意的是,所制备的苯并杂嗪树脂具有良好的耐热阻燃性能,玻璃化温度为302℃,800℃时炭收率为56.5%,极限氧指数为40.10,放热能力为30.9 J/g K,总放热量为2.9 KJ/g, UL-94 V-0等级。此外,聚合物(SF-f)还表现出低介电常数(2.73,5 GHz; 2.68, 10 GHz)和低介电损耗(0.0064,5 GHz; 0.0062, 10 GHz),这是由于交联密度增加,氢键增强,分子极性降低所致。因此,本研究不仅为设计和制备具有高热稳定、固有阻燃、超高频低介电性能的希夫碱生物苯并恶嗪树脂提供了一种有效的方法,而且为高性能苯并恶嗪化学的发展提供了新的思路。
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引用次数: 0
Photo-photo dual-cured vitrimer based on cardanol and glycerol derivatives 以腰果酚和甘油衍生物为基础的光固化双聚物
IF 5.1 3区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2026-01-16 DOI: 10.1016/j.reactfunctpolym.2026.106655
Austeja Leimontaite , Aysu Nasiribouyony , Sigita Grauzeliene , Kastytis Pamakstys , Visvaldas Varzinskas , Jolita Ostrauskaite
This work presents the first photo-photo dual-curable vitrimer resin, representing a difference from previously reported dual-curable vitrimer resins that relied on photo-thermal curing of acrylate-epoxy formulations. The design, synthesis and characterization of a vitrimer based on cardanol and glycerol derivatives were performed. A life cycle assessment has shown that the fossil carbon footprint of epoxy cardanol resin NC-514S is 1.6 times lower than that of bisphenol A-based epoxy resins, confirming its suitability as a bio-based alternative to petroleum-based epoxy resin. Dual-curable resin compositions containing epoxidized cardanol resin NC-514S, different glycerol-based acrylates, and thiol pentaerythritol tetrakis(3-mercaptopropionate) were formulated to ensure both simultaneous cationic and radical photopolymerization. Photocuring kinetics studies revealed an optimal resin with viscosity and rheological characteristics close to those of common commercial 3D printing resins. The optimized resin containing 20 wt% of epoxidized cardanol resin NC-514S, 20 wt% of glycerol 1,3-diglycerolate diacrylate, 40 wt% of 2-hydroxy-3-phenoxypropyl acrylate, and 20 wt% of pentaerythritol tetrakis(3-mercaptopropionate demonstrated vitrimeric properties, including shape-memory recovery within 120 s above the topology freezing temperature and glass transition temperature, self-welding with a 76% increase in tensile strength and a 125% increase in Young's modulus after self-welding, and reprocessability with mechanical properties retained after 3 reprocessing cycles. These results demonstrate that synthesized vitrimer is a promising material for reconfigurable or reusable packaging and packaging component applications, as well as various other adaptive structures and devices, while supporting sustainable use in reprocessable materials and circular economy applications.
这项工作提出了第一个光-光双固化玻璃体树脂,代表不同于以前报道的双固化玻璃体树脂依赖于丙烯酸酯-环氧树脂的光热固化配方。以腰果酚和甘油衍生物为基础,设计、合成和表征了一种玻璃聚合物。一项生命周期评估表明,环氧腰果酚树脂NC-514S的化石碳足迹比双酚基环氧树脂低1.6倍,证实了其作为石油基环氧树脂生物基替代品的适用性。双固化树脂组合物含有环氧腰果酚树脂NC-514S,不同的甘油基丙烯酸酯和巯基季戊四醇四酯(3-巯基丙酸),以确保同时进行阳离子和自由基光聚合。光固化动力学研究表明,最佳树脂的粘度和流变特性接近于普通的商用3D打印树脂。优化后的树脂含有20 wt%的环氧果酚树脂cs - 514s、20 wt%的甘油1,3-二甘油酯二丙烯酸酯、40 wt%的2-羟基-3-苯氧丙酯和20 wt%的季戊四醇四甲基(3-巯基丙酸),具有玻璃化性能,包括在拓扑冻结温度和玻璃化转变温度以上120 s内形状记忆恢复,自焊接后抗拉强度提高76%,杨氏模量提高125%。再加工性能,经3次再加工循环后仍保持机械性能。这些结果表明,合成玻璃体是一种很有前途的材料,可用于可重构或可重复使用的包装和包装组件应用,以及各种其他自适应结构和设备,同时支持可再加工材料的可持续使用和循环经济应用。
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引用次数: 0
Synergistic toughening of polypropylene using recycled PVB and POE-g-MA via one-step reactive blending 回收PVB与POE-g-MA一步反应共混增韧聚丙烯的研究
IF 5.1 3区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2026-01-15 DOI: 10.1016/j.reactfunctpolym.2026.106653
Jingjing An , Rui Wang , Jianfeng Wang , Yanyu Yang , Wanjie Wang , Yanxia Cao
In this study, recycled poly(vinyl butyral) (r-PVB) and maleic anhydride grafted poly(ethylene-octene) (POE-g-MA) were employed to synergistically toughen polypropylene (PP) via one-step reactive melt blending. Results revealed that hydroxyl groups of r-PVB reacted with anhydride groups of POE-g-MA at the interface, generating in situ compatibilizers and significantly improving interfacial adhesion. Although thermodynamic predictions suggested that POE-g-MA should encapsulate r-PVB, the actual morphology was dominated by viscosity-driven kinetics, leading to the formation of a unique core-shell structure with r-PVB as the shell and POE-g-MA as the core. This morphology effectively promoted energy dissipation, enabling the PP/r-PVB/POE-g-MA (70/10/20) blend to achieve a notched impact strength of 78.0 kJ/m2, which is 16.6 times higher than that of neat PP, thus realizing super-toughening. This work not only provides a new pathway for value-added recycling of r-PVB but also reveals a kinetic-dominated mechanism of phase morphology in reactive multicomponent blends.
本研究利用再生聚乙烯醇丁醛(r-PVB)和马来酸酐接枝聚乙烯-辛烯(POE-g-MA),通过一步反应熔融共混对聚丙烯(PP)进行增韧。结果表明,r-PVB的羟基与POE-g-MA的酸酐基团在界面处发生反应,生成了原位相容剂,显著提高了界面的附着力。尽管热力学预测表明POE-g-MA应该包裹r-PVB,但实际形态是由粘度驱动的动力学主导的,导致形成了以r-PVB为壳,POE-g-MA为核的独特核壳结构。这种形态有效地促进了能量的耗散,使PP/r-PVB/POE-g-MA(70/10/20)共混物的缺口冲击强度达到78.0 kJ/m2,是纯PP的16.6倍,实现了超增韧。这项工作不仅为r-PVB的增值回收提供了新的途径,而且揭示了反应性多组分共混物中以动力学为主导的相形态机制。
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引用次数: 0
Synthesis and characterization of biomimetic hybrid membranes based on a side chain liquid crystalline poly(2-oxazoline) for selective proton transport 基于侧链液晶聚(2-恶唑啉)选择性质子输运仿生杂化膜的合成与表征
IF 5.1 3区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2026-01-14 DOI: 10.1016/j.reactfunctpolym.2026.106652
Jordi Guardià , Krzysztof Artur Bogdanowicz , José Antonio Reina , Marta Giamberini , Agnieszka Iwan , Xavier Montané
Designing biomimetic membranes with controlled and selective ion transport pathways is essential for next-generation electrochemical and energy-conversion systems. In this work, the cation transport properties of hybrid membranes composed of a side chain liquid crystalline poly(2-oxazoline), poly(2-(3,4,5-tris(4-dodecyloxybenzyloxy)phenyl)-2-oxazoline (PTOx40), supported on a polyester fabric were investigated. Polymer columns were homeotropically oriented by thermal treatment. X-ray diffraction revealed that hydrophobic substrates (fluorinated ethylene propylene resin and silanized glass) promoted better homeotropic orientation of the polymer columns than hydrophilic substrates (untreated glass). Wettability studies indicated comparable absorption behaviour for water and methanol in all membranes. Methanol uptake was consistently lower than that of water, highlighting their suitability for methanol-based hydrogen systems. Compared with Nafion® 117, these PTOx40-based membranes exhibited superior dimensional stability and a hydrophobic character. Cation transport was examined through electrochemical impedance spectroscopy (EIS), permeability tests, and linear sweep voltammetry (LSV). Although EIS confirmed the non-ionic nature of these membranes, LSV measurements demonstrated that oriented membranes exhibited lower resistance densities than unoriented ones. This strong dependence on column alignment underscores the role of columnar self-assembly in facilitating selective ion transport. The PTOx40-based membranes exhibited lower absolute conductivity than Nafion® 117. However, they showed remarkable proton selectivity, highlighting their potential for proton-transfer applications in artificial photosynthesis and sustainable energy technologies.
设计具有可控和选择性离子传输途径的仿生膜对于下一代电化学和能量转换系统至关重要。本文研究了侧链液晶聚(2-恶唑啉)、聚(2-(3,4,5-三(4-十二烷基氧基苯氧基)苯基)-2-恶唑啉(PTOx40)杂化膜在涤纶织物上的阳离子传输特性。聚合物柱经热处理后呈同向异性取向。x射线衍射表明,疏水基质(氟化乙烯丙烯树脂和硅化玻璃)比亲水基质(未经处理的玻璃)促进了聚合物柱的同向取向。润湿性研究表明,所有膜对水和甲醇的吸收行为相当。甲醇的吸收量始终低于水的吸收量,突出了它们对甲醇基氢系统的适用性。与Nafion®117相比,这些ptox40基膜具有优越的尺寸稳定性和疏水性。通过电化学阻抗谱(EIS)、渗透性测试和线性扫描伏安法(LSV)检测阳离子输运。虽然EIS证实了这些膜的非离子性质,但LSV测量表明,取向膜的电阻密度比无取向膜低。这种对柱排列的强烈依赖强调了柱自组装在促进选择性离子传输中的作用。ptox40基膜的绝对电导率低于Nafion®117。然而,它们表现出显著的质子选择性,突出了它们在人工光合作用和可持续能源技术中质子转移应用的潜力。
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引用次数: 0
Silane oligomer modified SiC and its application in polysilazane-based high-temperature resistant electrical insulation coatings 硅烷低聚物改性SiC及其在聚硅氮烷基耐高温电绝缘涂料中的应用
IF 5.1 3区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2026-01-14 DOI: 10.1016/j.reactfunctpolym.2026.106651
Zhaoqun Pan, Zhiliang Shen, Ming Zhong
To satisfy the synergistic protection requirements of oxidation resistance and electrical insulation for copper substrates in high-temperature environments, this study developed a polysilazane-based composite coating with high-temperature resistance and electrical insulation properties. The composite protective coating was formulated with polysilazane serving as the matrix resin and silicon carbide (SiC) as the functional filler. Meanwhile, an oligomer modifier (DMS-560) was synthesized via the hydrolysis-condensation of dimethyldiethoxysilane (KH−212) and γ-glycidoxypropyltrimethoxysilane (KH-560) for SiC surface modification, which effectively improved the interfacial compatibility between SiC filler and the polysilazane matrix. Furthermore, SiC underwent hydroxylation treatment using hydrogen peroxide to increase the number of surface-active sites, thereby enhancing the grafting efficiency of the oligomer modifier. The chemical structural alterations of SiC powder before and after modification were analyzed using Fourier-transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The microstructural morphology of the resultant coatings was characterized by scanning electron microscopy (SEM), and their key properties—including high-temperature resistance, hydrophobicity, hardness, and electrical insulation—were systematically evaluated. The findings indicate that the modified SiC demonstrates significantly enhanced dispersibility within the coating, with a notable reduction in agglomeration. The coating maintains its structural integrity after exposure to high-temperature conditions at 750 °C for 30 min, exhibiting excellent hydrophobicity and high hardness (maintaining a hardness of 7H after baking at 750 °C), as well as superior electrical insulation. This study concludes that surface modification using the silane oligomer modifier effectively optimizes SiC filler dispersion and interfacial bonding, thus realizing the synergistic enhancement of thermal resistance and electrical-mechanical protective properties of the polysilazane/SiC composite coating.
为了满足高温环境下铜基材抗氧化和电绝缘的协同保护要求,本研究开发了一种具有耐高温和电绝缘性能的聚硅氮烷基复合涂层。以聚硅氮烷为基体树脂,碳化硅为功能填料,配制了复合防护涂层。同时,通过二甲基二氧基硅烷(KH−212)和γ-缩水氧基丙基三甲氧基硅烷(KH-560)的水解缩合,合成了一种低聚改性剂DMS-560,用于SiC表面改性,有效地改善了SiC填料与聚硅氮烷基体的界面相容性。此外,用过氧化氢对SiC进行羟基化处理,增加了表面活性位点的数量,从而提高了低聚物改性剂的接枝效率。利用傅里叶变换红外光谱(FT-IR)和x射线光电子能谱(XPS)分析了改性前后SiC粉末的化学结构变化。通过扫描电镜(SEM)表征了涂层的微观结构形态,并对其关键性能(包括耐高温、疏水性、硬度和电绝缘性)进行了系统评价。结果表明,改性后的碳化硅在涂层内的分散性明显增强,团聚现象明显减少。该涂层在750℃高温条件下暴露30 min后仍保持其结构完整性,具有优异的疏水性和高硬度(750℃烘烤后硬度保持7H),以及优异的电绝缘性。本研究表明,硅烷低聚物改性剂的表面改性有效地优化了SiC填料的分散和界面键合,从而实现了聚硅烷/SiC复合涂层耐热性和机电防护性能的协同增强。
{"title":"Silane oligomer modified SiC and its application in polysilazane-based high-temperature resistant electrical insulation coatings","authors":"Zhaoqun Pan,&nbsp;Zhiliang Shen,&nbsp;Ming Zhong","doi":"10.1016/j.reactfunctpolym.2026.106651","DOIUrl":"10.1016/j.reactfunctpolym.2026.106651","url":null,"abstract":"<div><div>To satisfy the synergistic protection requirements of oxidation resistance and electrical insulation for copper substrates in high-temperature environments, this study developed a polysilazane-based composite coating with high-temperature resistance and electrical insulation properties. The composite protective coating was formulated with polysilazane serving as the matrix resin and silicon carbide (SiC) as the functional filler. Meanwhile, an oligomer modifier (DMS-560) was synthesized via the hydrolysis-condensation of dimethyldiethoxysilane (KH−212) and γ-glycidoxypropyltrimethoxysilane (KH-560) for SiC surface modification, which effectively improved the interfacial compatibility between SiC filler and the polysilazane matrix. Furthermore, SiC underwent hydroxylation treatment using hydrogen peroxide to increase the number of surface-active sites, thereby enhancing the grafting efficiency of the oligomer modifier. The chemical structural alterations of SiC powder before and after modification were analyzed using Fourier-transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The microstructural morphology of the resultant coatings was characterized by scanning electron microscopy (SEM), and their key properties—including high-temperature resistance, hydrophobicity, hardness, and electrical insulation—were systematically evaluated. The findings indicate that the modified SiC demonstrates significantly enhanced dispersibility within the coating, with a notable reduction in agglomeration. The coating maintains its structural integrity after exposure to high-temperature conditions at 750 °C for 30 min, exhibiting excellent hydrophobicity and high hardness (maintaining a hardness of 7H after baking at 750 °C), as well as superior electrical insulation. This study concludes that surface modification using the silane oligomer modifier effectively optimizes SiC filler dispersion and interfacial bonding, thus realizing the synergistic enhancement of thermal resistance and electrical-mechanical protective properties of the polysilazane/SiC composite coating.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106651"},"PeriodicalIF":5.1,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079084","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Dual triumph over thermal and dielectric constraints: Nitrile-functionalized POSS revolutionizes phthalonitrile for extreme environments 热和介电限制的双重胜利:腈功能化POSS彻底改变了极端环境下的邻苯二腈
IF 5.1 3区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2026-01-13 DOI: 10.1016/j.reactfunctpolym.2026.106650
Beibei Ji , Qiyong Xu , Yue Pan, Ke Duan, Wei Liao, Changping Yin, Suli Xing, Nan Wu
The pursuit of higher performance in the aerospace industry is pushing the limits of resin-based wave-transparent composites, demanding superior thermal resistance and lower dielectric constants. However, simultaneously optimizing thermal and dielectric performance in polymer matrices remains challenging due to their inherent trade-off. In this study, a novel polyhedral oligomeric silsesquioxane (POSS) monomer end-capped with phthalonitrile groups, TtSPPN, was synthesized and employed as an organic-inorganic copolymerization modifier to a baseline phthalonitrile resin (BPh). Results indicate that TtSPPN exhibited superior thermal stability, with a 5% thermal decomposition temperature (Td5%) exceeding 500 °C. Owing to its terminal phthalonitrile groups, the modifier enables molecular-level dispersion and participates in copolymerization cross-linking. The copolymers demonstrated exceptional thermal properties, with a Td5% reaching 584 °C and a glass transition temperature above 500 °C. Additionally, the incorporation of 5 wt% TtSPPN significantly reduced the dielectric constant and dielectric loss of the composite to 3.28 and 0.007 at 12 GHz, respectively, compared to 3.54 and 0.013 for pure BPh resin. Notably, the addition of TtSPPN into the cured samples significantly decreased water absorption. This study presents a novel design strategy for PN resins specifically engineered for extreme environments, demonstrating transformative potential for applications in high-performance composite materials.
航空航天工业对更高性能的追求正在推动树脂基波透明复合材料的极限,要求优越的热阻和更低的介电常数。然而,同时优化聚合物基体的热性能和介电性能仍然具有挑战性,因为它们具有内在的权衡。本研究合成了一种末端为邻苯二腈基团的新型多面体低聚硅氧烷(POSS)单体TtSPPN,并将其作为邻苯二腈基树脂(BPh)的有机-无机共聚改性剂。结果表明,TtSPPN具有良好的热稳定性,其5%的热分解温度(Td5%)超过500℃。由于其末端的邻苯二腈基团,该改性剂可以实现分子水平的分散,并参与共聚交联。共聚物表现出优异的热性能,Td5%达到584℃,玻璃化转变温度高于500℃。此外,掺入5 wt%的TtSPPN显著降低了复合材料的介电常数和介电损耗,在12 GHz分别为3.28和0.007,而纯BPh树脂为3.54和0.013。值得注意的是,TtSPPN的加入显著降低了固化样品的吸水率。本研究提出了一种专门为极端环境设计的新型PN树脂设计策略,展示了高性能复合材料应用的变革潜力。
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引用次数: 0
Structure–reactivity relationships in DDQ-based charge-transfer complexes: Single-crystal XRD, spectroscopic, DFT studies and photoinitiation efficiency in cationic polymerization ddq基电荷转移配合物的结构-反应性关系:单晶XRD,光谱,DFT研究和阳离子聚合中的光引发效率
IF 5.1 3区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2026-01-12 DOI: 10.1016/j.reactfunctpolym.2026.106649
Huseyin Cem Kiliclar , Berkay Sütay , Palani Natajaran , Onder Metin , Yusuf Yagci , Kerem Kaya
Charge-transfer (CT) cocrystals of the strong π-acceptor 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) with a series of aromatic electron donor molecules, namely, N-ethylcarbazole (NEC), p-dimethoxybenzene (DMB) and diphenylacetylene (DPA), were prepared for the first time by solvent evaporation method and characterized by single-crystal X-ray diffraction, UV–Vis, NMR spectroscopy and theoretical studies. According to conducted measurements, all complexes crystallize in 1:1 donor–acceptor stoichiometry, with nearly planar π-systems that stack in alternating columns. While NEC-DDQ and DMB-DDQ pairs form strong face-to-face π–π stacks with centroid–centroid distances of 3.28 Å and 3.39 Å, respectively, DPA–DDQ complex shows a slipped geometry with partial overlap (larger shift distance) and weaker π–π interaction with centroid-centroid distance of 3.84 Å. NEC and DMB donors exhibited photoinitiation in the cationic polymerizations of cyclohexene oxide (CHO) and isobutyl vinyl ether (IBVE), under visible, white and near-infrared irradiation, attributed to their high electron-donating ability and favorable co-facial stacking with DDQ. In contrast, DPA-DDQ complex failed to initiate photocationic polymerization due to weak donor strength and poor π–π stacking. No complexes initiated ε-caprolactone (ECL) polymerization, indicating a need for stronger Lewis acid for the initiation. This study provides design principles for engineering solid-state CT photoinitiators via donor choice and crystal packing.
采用溶剂蒸发法制备了强π受体2,3-二氯-5,6-二氰-1,4-苯醌(DDQ)与n -乙基咔唑(NEC)、对二甲氧基苯(DMB)和二苯乙炔(DPA)的电荷转移(CT)共晶,并通过单晶x射线衍射、紫外可见光谱、核磁共振光谱和理论研究对其进行了表征。根据进行的测量,所有配合物结晶在1:1的供体-受体化学计量,与近平面π系统,堆叠在交替列。NEC-DDQ复合物和DMB-DDQ复合物在质心-质心距离分别为3.28 Å和3.39 Å时形成了强的面对π -π叠加,而DPA-DDQ复合物在质心-质心距离为3.84 Å时呈现出部分重叠(移位距离较大)和较弱的π -π相互作用的滑移几何。在可见光、白光和近红外照射下,NEC和DMB给体在环氧环己烯(CHO)和异丁基乙烯基醚(IBVE)的阳离子聚合中表现出光引发反应,这是由于它们具有较高的给电子能力和与DDQ良好的共面堆积。相比之下,DPA-DDQ配合物由于给体强度较弱和π -π堆积较差而无法引发光催化聚合。没有配合物引发ε-己内酯(ECL)聚合,表明需要较强的Lewis酸引发。该研究通过供体选择和晶体包装为工程固态CT光引发剂提供了设计原则。
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引用次数: 0
Smart supramolecular hydrogels as a potential platform for wound dressings: Harnessing thiamine to boost neomycin efficacy 智能超分子水凝胶作为伤口敷料的潜在平台:利用硫胺素提高新霉素的功效
IF 5.1 3区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2026-01-12 DOI: 10.1016/j.reactfunctpolym.2026.106648
Alexandra Lupu , Luiza Madalina Gradinaru , Maria Bercea , Mihaela Avadanei , Vasile Robert Gradinaru , Irina Rosca , Daniela Rusu
Novel water-soluble thermoresponsive polyurethanes containing Pluronic F127 and lysine- or hexametylene-based diisocyanate are synthesized via a controlled polymerization approach. Subsequently, composite hydrogels of poly(vinyl alcohol) (PVA) and polyurethane (PU) are prepared and their morphological and rheological characteristics are systematically investigated. These physical networks are built through the combined action of two types of non-covalent interactions: hydrogen bonding (applying successive freezing/thawing cycles leads to the formation of a PVA network structure), and temperature-induced hydrophobic interactions (thermostating the samples at 37 °C changes the hydrophobic/hydrophilic balance and favors the gelation of PU micelles). This dual reinforcement strategy enhances the structural integrity and responsiveness of the composite matrix. The hydrogels are loaded with thiamine and neomycin sulfate to study their delivery in phosphate-buffered saline solution at pH = 7.4 and physiological temperature. In the presence of polyurethane, the release profile is dominated by both diffusional and relaxation contributions. The incorporation of different concentrations of a model active vitamin enhances the antibiotic delivery, but has no influence on the antimicrobial activity. Thus, this study opens a new window for the design of suitable eco-friendly biomaterials for wound dressing applications.
通过控制聚合方法合成了含有Pluronic F127和赖氨酸或六亚甲基二异氰酸酯的新型水溶性热敏聚氨酯。随后,制备了聚乙烯醇(PVA)和聚氨酯(PU)的复合水凝胶,并对其形态和流变特性进行了系统的研究。这些物理网络是通过两种非共价相互作用的共同作用建立的:氢键(施加连续的冷冻/解冻循环导致PVA网络结构的形成)和温度诱导的疏水相互作用(在37°C下加热样品改变疏水/亲水平衡,有利于PU胶束的凝胶化)。这种双重加固策略提高了复合材料基体的结构完整性和响应性。将硫胺素和硫酸新霉素装入水凝胶,研究其在pH = 7.4和生理温度下在磷酸盐缓冲盐水溶液中的传递。在聚氨酯存在的情况下,释放曲线主要由扩散和弛豫两种作用主导。不同浓度的模型活性维生素的掺入增强了抗生素的传递,但对抗菌活性没有影响。因此,本研究为设计适合伤口敷料应用的生态友好型生物材料打开了新的窗口。
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引用次数: 0
Exploring the use of pH-responsive alginate, cellulose nanocrystal and organosilane hybrid hydrogels for controlled berberine release 探索使用ph响应藻酸盐、纤维素纳米晶和有机硅烷混合水凝胶来控制小檗碱的释放
IF 5.1 3区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2026-01-10 DOI: 10.1016/j.reactfunctpolym.2026.106646
Elizangela Hafemann Fragal , Kamila Augusta Leão de Oliveira , Elisangela Pacheco da Silva , Karina Miyuki Retamiro , Celso Vataru Nakamura , Rafael Silva , Elias Basile Tambourgi , Adley Forti Rubira
A natural bioactive compound named berberine (Ber) has shown high therapeutic potential for chronic diseases, but suffers from extremely low gastrointestinal absorption, which limits its clinical application. In this work, we developed pH-responsive hybrid hydrogels based on sodium alginate (SA), cellulose nanocrystals (CNC), and 3-(trimethoxysilyl)propyl methacrylate (TMSPM) to enhance the intestinal bioavailability of Ber. The synthesis approach involved vinyl-functionalizing the SA and CNC to enable covalent crosslinking with the TMSPM via free-radical polymerization. Infrared spectroscopy confirmed the formation mechanism of the hybrid network, revealing covalent linkages (C-C, Si-O-C, and Si-O-Si) and non-covalent interactions (hydrogen bonding) among SA, CNC, and TMSPM. The hydrogel composed of SA containing 10% of CNC and 10% of TMPSM showed a Young's modulus 1.8-fold higher than that of the hydrogel containing 100% of SA. Swelling and release studies exhibited strong pH responsiveness, with sustained release at pH 7.4 (simulated intestinal fluid, SIF) and reduced diffusion at pH 1.2 (simulated gastric fluid, SGF). The optimized formulations sustained Ber release for up to 150 h, achieving 70–80% release at pH 7.4. The release of Ber was governed by super transport case II at pH 1.2 (faster release) and anomalous transport at pH 7.4 in a slower release, as confirmed by a reduced release rate constant. Cytotoxicity tests using the L929 fibroblast assay confirmed the biocompatibility of these hydrogels, supporting their potential as long-term, pH-responsive carriers for intestinal drug delivery and controlled therapeutic release.
一种名为小檗碱(berberine, Ber)的天然生物活性化合物对慢性疾病显示出很高的治疗潜力,但由于其胃肠道吸收极低,限制了其临床应用。在这项工作中,我们开发了基于海藻酸钠(SA)、纤维素纳米晶体(CNC)和3-(三甲氧基硅基)甲基丙烯酸丙酯(TMSPM)的ph响应型混合水凝胶,以提高Ber的肠道生物利用度。合成方法包括乙烯基功能化SA和CNC,通过自由基聚合使其与TMSPM共价交联。红外光谱证实了杂化网络的形成机制,揭示了SA、CNC和TMSPM之间的共价键(C-C、Si-O-C和Si-O-Si)和非共价相互作用(氢键)。含有10% CNC和10% TMPSM的SA组成的水凝胶的杨氏模量比含有100% SA的水凝胶的杨氏模量高1.8倍。肿胀和释放研究显示出强烈的pH响应性,在pH 7.4(模拟肠液,SIF)时持续释放,在pH 1.2(模拟胃液,SGF)时扩散减少。优化后的配方在pH 7.4条件下的释氢时间长达150 h,释氢量达到70-80%。通过降低的释放速率常数证实,Ber的释放受pH值1.2时的超转运情况II(快速释放)和pH值7.4时的异常转运情况II(较慢释放)控制。使用L929成纤维细胞试验的细胞毒性测试证实了这些水凝胶的生物相容性,支持它们作为肠道药物递送和控制治疗释放的长期ph响应载体的潜力。
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引用次数: 0
A versatile platform of Quinolinoxazine monomers and polymers: Unlocking structure-property relationships in thermal stability, biological activity, and white-light emission 喹啉恶嗪单体和聚合物的多功能平台:解锁热稳定性,生物活性和白光发射的结构-性质关系
IF 5.1 3区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2026-01-09 DOI: 10.1016/j.reactfunctpolym.2026.106647
Abdulsalam Mahdy , Jalal A. Zahra , Violet Kasabri , Randa N. Haddadin , Osama Younis
A novel and versatile platform of quinoline-based benzoxazine (quinolinoxazine) monomers and their corresponding polybenzoxazines has been developed to reveal deep insights into the structure–property correlations governing thermal robustness, biological functionality, and photophysical response. The monomers were synthesized from 8-hydroxyquinoline and a series of aliphatic diamines, thoroughly characterized via FTIR and NMR spectroscopy, and subsequently polymerized. The evolution of structure, curing dynamics, and thermal characteristics of the resulting polymers was comprehensively investigated through FTIR, DSC, and TGA analyses, while morphological and crystallographic features were examined using SEM and XRD. The results identified the diamine spacer length as a decisive factor in modulating polymer performance. Among them, Poly(QZ-C3), featuring a symmetric C3 linker, exhibited the highest glass transition temperature (Tg = 247 °C) and remarkable char yield (43%), correlating to an exceptional Limiting Oxygen Index (LOI) of 34.7%. Biological assays revealed compelling multifunctionality: Mono(QZ-C2) demonstrated broad-spectrum antimicrobial activity and high antioxidative DPPH radical scavenging capacities compared to the respective reference agents. Mono(QZ-C3) outperformed the reference NSAID indomethacin, exerting exceptional anti-inflammatory potency at the nanomolar level. All tested compounds displayed both selective cytotoxicity and differential anti-inflammatory/immunomodulatory physiologically regulated activities, outperforming the antineoplastic proapoptotic cisplatin in the majority of malignancy cell lines. None of the tested synthetic compounds exerted toxicity toward normal noncancerous cells (PDL fibroblasts or RAW264.7 macrophages), unlike cisplatin. Photoluminescence investigations further revealed concentration-dependent emission behavior in the monomers, resulting in solid-state white-light emission. Upon polymerization, the chromophores became effectively confined within the network, enabling excitation-dependent color tuning and stable white-light coordinates. Altogether, this study positions quinolinoxazines as a powerful multifunctional materials framework, deliberately integrating superior thermal stability, broad-spectrum bioactivity, and tunable luminescence through a unified molecular design, offering a strategic blueprint for the rational design of next-generation multifunctional polymers.
基于喹啉的苯并恶嗪(喹啉恶嗪)单体及其相应的聚苯并恶嗪的新型多功能平台已经开发出来,以揭示对控制热稳健性,生物功能和光物理响应的结构-性质相关性的深刻见解。以8-羟基喹啉和一系列脂肪族二胺为原料合成了这些单体,并通过FTIR和NMR进行了表征,随后进行了聚合。通过FTIR、DSC和TGA分析全面研究了聚合物的结构演变、固化动力学和热特性,并用SEM和XRD分析了聚合物的形态和晶体学特征。结果表明,二胺间隔段长度是调节聚合物性能的决定性因素。其中,具有对称C3连接体的Poly(QZ-C3)具有最高的玻璃化转变温度(Tg = 247°C)和显著的炭产率(43%),其极限氧指数(LOI)高达34.7%。生物试验显示了令人信服的多功能性:与各自的参比剂相比,Mono(QZ-C2)具有广谱抗菌活性和高抗氧化DPPH自由基清除能力。Mono(QZ-C3)优于参考非甾体抗炎药吲哚美辛,在纳摩尔水平上发挥了卓越的抗炎效力。所有被测试的化合物都显示出选择性细胞毒性和不同的抗炎/免疫调节生理调节活性,在大多数恶性细胞系中表现优于抗肿瘤促凋亡顺铂。与顺铂不同,所有被测试的合成化合物都没有对正常非癌细胞(PDL成纤维细胞或RAW264.7巨噬细胞)产生毒性。光致发光研究进一步揭示了单体的浓度依赖性发射行为,导致固态白光发射。聚合后,发色团被有效地限制在网络中,实现了依赖于激发的颜色调节和稳定的白光坐标。总之,本研究将喹啉恶嗪定位为一种强大的多功能材料框架,通过统一的分子设计,有意将优越的热稳定性、广谱生物活性和可调发光结合起来,为下一代多功能聚合物的合理设计提供了战略蓝图。
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Reactive & Functional Polymers
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