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| 1 | Supramolecular Polymer Networks with Enhanced Mechanical Properties:The Marriage of Covalent Polymer and Metallacycle显示文摘Main observation and conclusion Supramolecular polymer networks(SPNs)have always been the focus of research due to their novel features of good processability,stimuli-responsiveness,self-healing,and recyclability.Herein,we report the preparation of a metallacycle-linked supramolecular gel via orthogonal metal-ligand interactions and host-guest interactions.A triangular metallacycle with three appended 21-crown-7(21C7)units was obtained by the metal coordination of nickel(II)-salen-based dipyridyl ligands and platinum(II)acceptors.The integration of this metallacycle and traditional copolymer bearing secondary ammonium salts constructed a SPN via host-guest recognition between 21C7 units and ammonium salts,and a supramolecular gel further formed at high concentration.Multiple stimulus responsiveness and self-healing properties of gel were observed.The gel exhibited better stretchability compared to relative gel formed by copolymer alone owing to the synergistic effect of covalent bonds and supramolecular interactions.Moreover,compared to the model gel without metallacycles,the gel showed higher storage and loss moduli,and exhibited stronger stiffness in the self-healing tests performed with rheometer,indicating the metallacycle played an important role in improving the stiffness and self-healing of the gel.Therefore,the feasible approach to the formation of SPNs by the marriage of covalent polymers and metallacycles is expected to open a new way to design novel SPNs. | Yue-Yue Zhang Feng Chen Yang Li Hua-Yu Qiu Jin-Jin Zhang Shou-Chun Yin | 2021 | Chinese Journal of Chemistry2021,39,10: | 1 |
| 2 | Functional Materials with Pillarene Struts显示文摘Pillar[n]arenes(pillarenes for short)are a relatively new generation of macrocyclic host compounds with rigid cylinder architectures containing several hydroquinone units that are bridged by methylene(−CH2−)at their para positions.The investigation of pillarenes has expanded from the sole domain of supramolecular chemistry to invoke immense interest among scientists striving to exploit intelligent materials or functional systems,with regard to their fascinating attributes such as symmetric structures,tailorable functionalization,and unique host−guest properties.Over the past few years,researchers have focused on the construction of prominent supramolecular architectures such as supramolecular switches,supramolecular polymers,and self-assembled amphiphilic systems on the basis of host−guest chemistry in collaboration with other noncovalent interactions.One of the most attractive characteristics of these supramolecular assemblies relies on the tunable mechanical motions via switching of the most conformationally and thermally stable structures in a dynamic and reversible manner,which could be affected by the external conditions and enable the reciprocal effect with surrounding environments.Consequently,macrocyclic arenes are the key components of stimuli-responsive supramolecular assemblies,serving as important candidates in the construction of advanced supramolecular materials,including organic functional systems and organic−inorganic hybrid systems.In this Account,we present a relatively elaborate summary of the significant and typical intelligent systems containing pillarenes and their extended versions with a focus on our own contributions to this field during the past decade.Finally,in the last section of the review,challenges and perspectives are given. | Zheng Li Ying-Wei Yang | 2021 | Accounts of Materials Research2021,2,4: | 0 |
| 3 | 一种新型荧光聚氨酯的制备与研究显示文摘荧光聚氨酯在荧光聚合物研究领域中近年受到越来越多的关注,为了制备一种具有多功能的荧光聚氨酯,以1,5-二羟基萘为荧光功能单体,合成了一种新型的具有固态和酸碱响应荧光发射的多功能聚氨酯(MFU)。采用核磁共振(^1H NMR)、红外光谱(FTIR)、紫外-可见光谱(UV-vis)对其进行了结构表征,分别用溶液样品和固态薄膜样品在荧光分光光度计上研究了其荧光发光性质,还用酸碱滴加实验研究了MFU溶液样品的酸碱响应荧光性质。结果表明:核磁谱图在δ=7.20~7.54范围内出现萘环质子吸收峰,红外光谱在1630、1548、1483 cm^-1附近出现萘环骨架振动峰,可见-紫外吸收光谱中在226 nm处以及260~340 nm范围也出现萘环共轭吸收谱带;另外,选取紫外光谱中226 nm为基准,根据朗伯-比尔定律,用标准曲线法拟合定量分析可知,MFU分子链中荧光基团含量与理论计算基本一致;综合表明,分子链中含有功能基团1,5-二羟基萘的荧光聚氨酯被成功制备。荧光光谱表明,MFU样品无论是溶液状态还是固体状态,在460 nm左右宽范围内都有较强的荧光发射,而相对照的纯聚氨酯样品在两种状态下均没有明显的荧光发射。此外,溶液样品在酸(490 nm,蓝绿光)和碱(460 nm,蓝光)环境下具有不同的发光波长,最大位移超过30 nm;荧光强度方面,强碱性(pH=11)相对于强酸性(pH=3)环境下的荧光强度降低了89%。基于MFU溶液样品在酸碱环境中表现出发光颜色和发光强度的双特征响应行为,新型荧光聚氨酯MFU有望用于强酸和强碱的双信号探测。因此,通过化学键接引进荧光功能单体,成功制备了一种新型的具有固态和酸碱响应荧光发射的多功能聚氨酯。 | 彭青海 聂泽坤 蔡绪福 | 2021 | 工程科学与技术2021,53,1: | 0 |