刺激响应型AIE水凝胶研究进展 增强出版

{ "defaultlang": "zh", "titlegroup": { "articletitle": [ { "lang": "zh", "data": [ { "name": "text", "data": "刺激响应型AIE水凝胶研究进展" } ] }, { "lang": "en", "data": [ { "name": "text", "data": "Research Progress of Stimuli-responsive AIE-active Hydrogels" } ] } ] }, "contribgroup": { "author": [ { "name": [ { "lang": "zh", "surname": "温", "givenname": "雪菲", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "WEN", "givenname": "Xue-fei", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" } ], "role": [ "first-author" ], "bio": [ { "lang": "zh", "text": [ "温雪菲(1996-)，女，内蒙古达拉特旗人，硕士研究生，2019年于集宁师范学院获得学士学位，主要从事有机发光材料的合成及性能的研究。E-mail: 1097560502@qq.com" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019408&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019411&type=", "big": 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"http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019447&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019433&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019435&type=" } ], "data": [ [ { "name": "text", "data": "莎仁" }, { "name": "text", "data": "(1963-)，女，内蒙古呼和浩特人，学士，教授，硕士生导师，1985年于内蒙古师范大学获得学士学位，主要从事发光材料、光致变色材料的设计合成及应用的研究。E-mail: " }, { "name": "text", "data": "sr@imnu.edu.cn" } ] ] } ], "email": "sr@imnu.edu.cn", "deceased": false }, { "name": [ { "lang": "zh", "surname": "王", "givenname": "建国", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "WANG", "givenname": "Jian-guo", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff2", "text": "2" } ], "role": [ "corresp" ], "corresp": [ { "rid": "cor2", "lang": "en", "text": "wangjg@imu.edu.cn", "data": [ { "name": "text", "data": "wangjg@imu.edu.cn" } ] } ], "bio": [ { "lang": "zh", "text": [ "王建国(1982-)，男，内蒙古兴和人，博士，教授，博士生导师，2014年于中国科学院化学研究所获得博士学位，主要从事有机光电功能材料的研究。E-mail: wangjg@iccas.ac.cn" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019455&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019473&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019461&type=" } ], "data": [ [ { "name": "text", "data": "王建国" }, { "name": "text", "data": "(1982-)，男，内蒙古兴和人，博士，教授，博士生导师，2014年于中国科学院化学研究所获得博士学位，主要从事有机光电功能材料的研究。E-mail: " }, { "name": "text", "data": "wangjg@iccas.ac.cn" } ] ] } ], "email": "wangjg@iccas.ac.cn", "deceased": false } ], "aff": [ { "id": "aff1", "intro": [ { "lang": "zh", "label": "1", "text": "内蒙古师范大学　化学与环境科学学院，内蒙古　呼和浩特　010022", "data": [ { "name": "text", "data": "内蒙古师范大学　化学与环境科学学院，内蒙古　呼和浩特　010022" } ] }, { "lang": "en", "label": "1", "text": "College of Chemistry and Environmental Science, Inner Mongolia Normal University, Hohhot 010022, China", "data": [ { "name": "text", "data": "College of Chemistry and Environmental Science, Inner Mongolia Normal University, Hohhot 010022, China" } ] } ] }, { "id": "aff2", "intro": [ { "lang": "zh", "label": "2", "text": "内蒙古大学　化学化工学院，内蒙古精细有机合成重点实验室，内蒙古　呼和浩特　010021", "data": [ { "name": "text", "data": "内蒙古大学　化学化工学院，内蒙古精细有机合成重点实验室，内蒙古　呼和浩特　010021" } ] }, { "lang": "en", "label": "2", "text": "Inner Mongolia Key Laboratory of Fine Organic Synthesis, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China", "data": [ { "name": "text", "data": "Inner Mongolia Key Laboratory of Fine Organic Synthesis, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "刺激响应水凝胶可以对环境的微小变化产生较大的物理化学变化，在药物传递、生物分离、生物传感器和组织工程等领域具有广泛的应用。但受聚集导致荧光猝灭（ACQ）效应的影响，其在发光相关领域的应用受到限制，聚集诱导发光（AIE）概念的提出解决了这一难题。将AIE分子引入水凝胶体系，获得刺激响应型AIE水凝胶，在生物医学、信息防伪、3D水凝胶驱动器以及软体机器人的开发等多个高科技领域崭露头角。本文将近年来报道的刺激响应型AIE水凝胶按刺激因素分为物理因素（温度和光）、化学因素（pH、溶剂和离子）和生物因素（酶）三大类，分别阐述了水凝胶的制备、响应机理及潜在应用，并针对刺激响应型AIE水凝胶面临的问题和挑战进行了展望。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "Stimulus-responsive hydrogels, which can undergo physical and/or chemical changes in response to the minor variations in the environment, are widely applied in the fields of drug delivery, bioseparation, biosensors and tissue engineering. However, due to the aggregation-caused quenching(ACQ) of fluorescence, their applications in luminescence-related fields are extremely limited. Fortunately, aggregation-induced emission(AIE) phenomena perfectly resolved the problem. By incorporating fluorophores with AIE feature into hydrogels, stimuli-responsive AIE-active hydrogels can be obtained. And they have cut a figure in several high-tech fields including biomedical, information anti-counterfeiting, 3D hydrogel actuators and soft robots. In this article, we summarized and classified the recently reported stimuli-responsive AIE-active hydrogels into three categories: those are responsive to physical(temperature and light), chemical(pH, solvent and ion type) and biological(enzyme) stimulus. The preparation, responsive mechanism and applications of these stimuli-responsive AIE-active hydrogels were described respectively. And finally, the problems and challenges faced by stimuli-responsive AIE-active hydrogels are also prospected." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "刺激响应型水凝胶" } ], [ { "name": "text", "data": "聚集诱导发光" } ], [ { "name": "text", "data": "信息防伪" } ], [ { "name": "text", "data": "软体机器人" } ], [ { "name": "text", "data": "药物传递" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "stimuli-responsive hydrogels" } ], [ { "name": "text", "data": "aggregation-induced emission" } ], [ { "name": "text", "data": "information anti-counterfeiting" } ], [ { "name": "text", "data": "soft robots" } ], [ { "name": "text", "data": "drug delivery" } ] ] } ], "highlights": [], "body": [ { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "1" } ], "title": [ { "name": "text", "data": "引言" } ], "level": "1", "id": "s1" } }, { "name": "p", "data": [ { "name": "text", "data": "水凝胶是由低分子量分子通过共价/离子交联、络合和聚集等方式组装而成的具有三维网络结构的一类软材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "1", "type": "bibr", "rid": "R1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "3", "type": "bibr", "rid": "R3", "data": [ { "name": "text", "data": "3" } ] } } ], "rid": [ "R1", "R2", "R3" ], "text": "1-3", "type": "bibr" } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "，它具有吸水量大且不溶解的能力。根据水凝胶对外界刺激响应情况，可以把水凝胶分为普通水凝胶和智能水凝胶。普通水凝胶只能对所处环境中水含量的变化产生响应，经历吸水膨胀或失水收缩过程。而智能水凝胶可以对环境的微小变化产生较大的物理化学变化，如降解、溶胶-凝胶相变及形态改变等。而这些环境刺激因素包括物理因素(温度、光、电、超声、磁场等)、化学因素(pH值、溶剂、离子强度等)及生物因素(酶、抗体及糖)等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "4", "type": "bibr", "rid": "R4", "data": [ { "name": "text", "data": "4" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。因此智能水凝胶也可以称为刺激响应水凝胶。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "迄今为止，刺激响应水凝胶的应用范围已经随着科学家们的不断探索逐渐扩大，主要分布在药物传递、生物分离、生物传感器和组织工程四大领域" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "4", "type": "bibr", "rid": "R4", "data": [ { "name": "text", "data": "4" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "5", "type": "bibr", "rid": "R5", "data": [ { "name": "text", "data": "5" } ] } } ], "rid": [ "R4", "R5" ], "text": "4-5", "type": "bibr" } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。但其在发光相关领域的应用受到一定限制，这是因为发光水凝胶大部分是通过将发色团引入水凝胶材料中进行制备，但是许多发色团会在该过程中发生聚集导致荧光猝灭的现象(Aggregation-caused quenching,ACQ)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "6", "type": "bibr", "rid": "R6", "data": [ { "name": "text", "data": "6" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。在2001年，聚集诱导发光概念(Aggregation-induced emission,AIE)的提出为解决上述问题提供了方向" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "7", "type": "bibr", "rid": "R7", "data": [ { "name": "text", "data": "7" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } } ], "rid": [ "R7", "R8", "R9", "R10", "R11", "R12", "R13" ], "text": "7-13", "type": "bibr" } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。具有AIE性质的发色团在溶解状态时不发光，但是在多组分溶剂中，随着不良溶剂体积的增加，荧光随之增强。因为水凝胶基质具有亲水性，当把AIE分子引入其中时会自发聚集，从而限制其分子内运动使得荧光增强" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。因此，AIE分子的引入为构建刺激响应型水凝胶发光材料提供了可能性。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "到目前为止，刺激响应型AIE水凝胶的研究已经取得了一定的成果，根据其刺激响应类型，可将其分为物理刺激(温度刺激响应、光刺激响应)、化学刺激(pH值刺激响应、溶剂刺激响应)以及生物刺激(酶刺激响应)三大方面。本篇综述对以上刺激响应型AIE水凝胶进行详细介绍，阐述其在生物、信息防伪、3D水凝胶驱动器以及软体机器人开发等多个高科技领域的应用，并进一步对刺激响应型AIE水凝胶的未来发展前景进行展望。希望本篇综述能够对刺激响应型AIE水凝胶的未来发展提供一定的指导和帮助。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2" } ], "title": [ { "name": "text", "data": "刺激响应型AIE水凝胶" } ], "level": "1", "id": "s2" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.1" } ], "title": [ { "name": "text", "data": "物理因素" } ], "level": "2", "id": "s2a" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.1.1" } ], "title": [ { "name": "text", "data": "温度刺激响应型AIE水凝胶" } ], "level": "3", "id": "s2a1" } }, { "name": "p", "data": [ { "name": "text", "data": "利用温度响应型材料制备的温敏型水凝胶以温度变化作为刺激源，是一种非常好的选择。首先温度刺激是一种比较干净高效的刺激手段，不会向体系中引入其他物质从而影响输出信号；其次，基于现有的技术可以很精确地调控温度从而达到对光强度和颜色的精确控制。除此之外，温敏型水凝胶由于其良好的生物相容性，使其在生物医学方面研究较为广泛。在生物体中，自我修复是活体组织最基本的特性之一，这一特性使它们能够承受反复的损伤。受此启发，开发具有热响应特性的自愈合水凝胶对于生物医学领域具有重大意义，因而受到了研究者的广泛关注。自愈合水凝胶在破裂后可以自动修复，提高了材料的使用寿命，并为材料科学开辟了一个重要的方向" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } } ], "rid": [ "R15", "R16", "R17" ], "text": "15-17", "type": "bibr" } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2019年，何颖娜课题组" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "利用交联诱导热响应机制设计了具有可逆热响应的自愈合水凝胶。如" }, { "name": "xref", "data": { "text": "图1(a)~(b)", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1(a)~(b)" } ] } }, { "name": "text", "data": "所示，这项研究通过调控双丙酮丙烯酰胺(DMA)和N,N-二甲基丙烯酰胺(DAA)用量的比例，并将四苯乙烯(TPE)作为AIE发光团键合在共聚物的末端，合成了四种具有不同聚合比的聚合物TPE-P(DMA-" }, { "name": "italic", "data": [ { "name": "text", "data": "stat" } ] }, { "name": "text", "data": "-DAA):TPE-P(DMA" }, { "name": "sub", "data": [ { "name": "text", "data": "187" } ] }, { "name": "text", "data": "-" }, { "name": "italic", "data": [ { "name": "text", "data": "stat" } ] }, { "name": "text", "data": "-DAA" }, { "name": "sub", "data": [ { "name": "text", "data": "20" } ] }, { "name": "text", "data": ")(A)、TPE-P(DMA" }, { "name": "sub", "data": [ { "name": "text", "data": "198" } ] }, { "name": "text", "data": "-" }, { "name": "italic", "data": [ { "name": "text", "data": "stat" } ] }, { "name": "text", "data": "-DAA" }, { "name": "sub", "data": [ { "name": "text", "data": "40" } ] }, { "name": "text", "data": ")(B)、TPE-P(DMA" }, { "name": "sub", "data": [ { "name": "text", "data": "199" } ] }, { "name": "text", "data": "-" }, { "name": "italic", "data": [ { "name": "text", "data": "stat" } ] }, { "name": "text", "data": "-DAA" }, { "name": "sub", "data": [ { "name": "text", "data": "59" } ] }, { "name": "text", "data": ")(C)、TPE-P(DMA" }, { "name": "sub", "data": [ { "name": "text", "data": "182" } ] }, { "name": "text", "data": "-" }, { "name": "italic", "data": [ { "name": "text", "data": "stat" } ] }, { "name": "text", "data": "-DAA" }, { "name": "sub", "data": [ { "name": "text", "data": "72" } ] }, { "name": "text", "data": ")(D)；然后将其分别与具有双酰肼单元的交联剂聚环氧乙烷(PEO" }, { "name": "sub", "data": [ { "name": "text", "data": "23" } ] }, { "name": "text", "data": "DH)或二硫代二丙酸二肼(DTDPH)反应，其中以PEO" }, { "name": "sub", "data": [ { "name": "text", "data": "23" } ] }, { "name": "text", "data": "DH为交联剂均获得了透明的水凝胶，而以DTDPH为交联剂则可分别获得透明(与共聚物A或B交联)和不透明(与共聚物C或D交联)两类水凝胶。所得水凝胶均具有热响应性，最低临界溶液温度(LCST)可调控至体温附近。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "(a)TPE-P(DMA-" }, { "name": "italic", "data": [ { "name": "text", "data": "stat" } ] }, { "name": "text", "data": "-DAA)的合成路线；(b)DTDPH做交联剂制备水凝胶；(c)共聚物C与PEO" }, { "name": "sub", "data": [ { "name": "text", "data": "23" } ] }, { "name": "text", "data": "DH或DTDPH交联形成的水凝胶自愈合过程：(ⅰ)自然光和紫外光下的水凝胶照片；(ⅱ)将小熊头形状的水凝胶耳朵部分剪下来；(ⅲ)将耳朵部分重新放置到小熊头形状的水凝胶上；(ⅳ)24 h后水凝胶自愈合结果；共聚物D/DTDPH(2∶1)溶液对小鼠表皮细胞(JB6 P+)(d)和海拉细胞(HeLa)(e)的体外细胞毒性(mean±SD," }, { "name": "italic", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "=6);(f)共聚物D/DTDPH(2∶1)水凝胶的DOX释放曲线(mean±SD," }, { "name": "italic", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "=3)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 1" } ], "title": [ { "name": "text", "data": "(a)The synthesis of TPE-P(DMA-" }, { "name": "italic", "data": [ { "name": "text", "data": "stat" } ] }, { "name": "text", "data": "-DAA). (b)Preparation of hydrogel by diacylhydrazide cross-linking. (c)Self-healing of the hydrogel formed by polymer C with PEO" }, { "name": "sub", "data": [ { "name": "text", "data": "23" } ] }, { "name": "text", "data": "DH or DTDPH cross-linking: (ⅰ)hydrogels in natural light and 365 nm UV light, (ⅱ)removing the ears from the bear head-shaped hydrogels, (ⅲ)reconnecting the ears to the bear head-shaped hydrogels, (ⅳ)self-healing result after 24 h of contact. " }, { "name": "italic", "data": [ { "name": "text", "data": "In vitro" } ] }, { "name": "text", "data": " cytotoxicity of the polymer D/DTDPH(2∶1) solution to JB6 P+ cells(d) and HeLa cells(e)(mean±SD, " }, { "name": "italic", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "=6). (f)The DOX release curves of the polymer D/DTDPH(2∶1) hydrogel(mean±SD, " }, { "name": "italic", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "=3)" }, { "name": "sup", "data": [ { "name": "text", "data": " [" }, { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019477&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019482&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019479&type=" } ] } }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图1(c)", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1(c)" } ] } }, { "name": "text", "data": "展示了以PEO" }, { "name": "sub", "data": [ { "name": "text", "data": "23" } ] }, { "name": "text", "data": "DH或DTDPH为交联剂与共聚合C反应制备的水凝胶的自愈过程。首先利用模具分别制备了小熊头形状的透明和不透明水凝胶。透明水凝胶在紫外光下发光微弱，而不透明水凝胶在紫外光下发出强烈的蓝光。将这两个透明或不透明的小熊头部的耳朵剪下来，重新放置到耳朵的位置上，或相互交换后再重新放置到耳朵的位置上。将水凝胶放回原模具中孵育24 h，用镊子夹住耳朵帮助其自愈。从图中可以观察到透明水凝胶中未经交换的小熊耳朵自愈合良好，而不透明水凝胶则没有自愈合效果。这是因为不透明水凝胶中可逆的酰腙键被包裹在疏水区域中，自愈反应受到限制。另外，无论是透明水凝胶还是不透明水凝胶，经相互交换的两只耳朵自愈性能良好，形成了异形外观的小熊头部形状的水凝胶。这是因为，虽然不透明水凝胶中酰腙键的反应受到限制，但是透明水凝胶中酰腙键的反应活性较高，加速了界面上酰腙键交换的整体反应速率。更为重要的是，在水凝胶形成和自愈过程中没有添加额外的催化剂或刺激因素，这无异于提高了水凝胶的生物兼容性。细胞毒性实验证实了这一点，" }, { "name": "xref", "data": { "text": "图1(d)~(e)", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1(d)~(e)" } ] } }, { "name": "text", "data": "结果显示水凝胶溶液对小鼠表皮细胞(JB6 P+)和海拉细胞(HeLa)无明显毒性。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "基于其热响应性质和发光性质，这类水凝胶有望成为理想的药物控释载体，可将抗癌药物阿霉素(DOX)负载到以DTDPH为交联剂、共聚物D制备的水凝胶中。" }, { "name": "xref", "data": { "text": "图1(f)", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1(f)" } ] } }, { "name": "text", "data": "显示，在pH=5.4、温度为37 ℃时，DOX释放速度明显快于pH=7.4时的释放速度。并且在pH=5.4时可100%释放，在pH=7.4时，释放率仅为63%。这是因为成胶过程中，DOX通过胺基与凝胶中共聚物的酮羰基发生反应形成亚胺键。pH值越低，亚胺键断裂越快，酰腙键交换速率越高，药物释放速率越高。由于肿瘤组织间pH值低于正常组织，因此这类热响应自愈合水凝胶将成为肿瘤治疗中局部药物递送和实时监测的有力工具。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "温敏水凝胶除了在生物方面的应用，在信息防伪中也大有作为。化学防伪利用带有发色团的材料或发光材料对信息进行加密，是一项非常有前景的防伪技术" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "19", "type": "bibr", "rid": "R19", "data": [ { "name": "text", "data": "19" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。到目前为止，科学家们已经开发了许多化学防伪材料，例如防伪油墨、多种类的聚合物薄膜材料等。但这些材料大都属于静态防伪材料，而开发具有动态颜色变化的发光材料则更具有挑战性。动态防伪材料具有按需解密的效果，从而可提高编码文本的安全性" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "20", "type": "bibr", "rid": "R20", "data": [ { "name": "text", "data": "20" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "22", "type": "bibr", "rid": "R22", "data": [ { "name": "text", "data": "22" } ] } } ], "rid": [ "R20", "R21", "R22" ], "text": "20-22", "type": "bibr" } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。但目前的研究主要集中在2D平台来实现信息加密。与传统的2D信息加密平台相比，3D信息加密平台更具有额外优势，包括更先进的加密算法、增强解码复杂性等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "23", "type": "bibr", "rid": "R23", "data": [ { "name": "text", "data": "23" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。但是，基于发光材料的三维信息加密在材料设计和制备方面仍极具挑战，而刺激响应型荧光高分子水凝胶(FPHs)综合了荧光材料和聚合物水凝胶的优点，具有解决这些问题的潜力" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "24", "type": "bibr", "rid": "R24", "data": [ { "name": "text", "data": "24" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } } ], "rid": [ "R24", "R25" ], "text": "24-25", "type": "bibr" } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。FPHs可以根据其化学结构和组成对外界刺激的敏感性以及动态荧光特性方便地定制。因此，荧光水凝胶近年来成为智能保密信息最突出的材料之一" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "29", "type": "bibr", "rid": "R29", "data": [ { "name": "text", "data": "29" } ] } } ], "rid": [ "R26", "R27", "R28", "R29" ], "text": "26-29", "type": "bibr" } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2021年，陈涛教授课题组" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "30", "type": "bibr", "rid": "R30", "data": [ { "name": "text", "data": "30" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "将AIE机制与金属-配体动态配位反应相结合，设计合成了多功能程序化聚合物水凝胶PAAD。该水凝胶具有多态荧光开关性质，可制备成更为强大的3D信息加密平台，用于信息按需解密和传输。如" }, { "name": "xref", "data": { "text": "图2(a)", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2(a)" } ] } }, { "name": "text", "data": "所示，PAAD水凝胶含有典型的双重网状结构：物理交联的琼脂网络和化学交联的poly(AAc-co-AAm-co-DAEAN)网络。其中poly(AAc-co-AAm-co-DAEAN)网络是由具有AIE性质的4-二甲氨基乙氧基-N-烯丙基-1,8-萘酰胺(DAEAN)与丙烯酸(AAc)、丙烯酰胺(AAm)、亚甲基双丙烯酰胺交联剂之间的自由基共聚反应制备的，具有最高临界溶液温度(UCST)。由于其疏水性及AIE性质，DAEAN在亲水性PAAD凝胶中会自发聚集，使得PAAD发出明亮的蓝色荧光。PAAD水凝胶中的丙烯酸基团与Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "发生络合后可形成Eu-PAAD水凝胶，导致DAEAN聚集程度增加，Eu-PAAD水凝胶的发光进一步增强(" }, { "name": "xref", "data": { "text": "图2(b)", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2(b)" } ] } }, { "name": "text", "data": ")。丙烯酸与Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "之间的动态可逆配位可充当短时交联，在室温下经形状记忆过程将水凝胶薄膜设计成复杂的3D短时结构。同时，得益于Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "配位聚合物的特殊结构，其结构中的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "配位作用和氢键经热刺激逐步断裂，使得Eu-PAAD水凝胶具有多态荧光开关性质(" }, { "name": "xref", "data": { "text": "图2(c)", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2(c)" } ] } }, { "name": "text", "data": ")。" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "(a)Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "络合法制备Eu-PAAD水凝胶；(b)PAAD和Eu-PAAD水凝胶的荧光光谱，插图照片在365 nm紫外灯下拍摄；(c)Eu-PAAD水凝胶在不同温度下的多态荧光开关机理示意图；(d)用手将2D信息载体弯折成3D形状并浸入Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "溶液中，将形状固定后获得的按需解密3D防伪平台示意图，该材料在不同温度下显示不同的信息：15 ℃(无信息),40 ℃(“木”),70 ℃(“村”)，完整信息(“树”)只有用EDTA诱导凝胶从3D结构恢复到2D结构时才能被解密" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "30", "type": "bibr", "rid": "R30", "data": [ { "name": "text", "data": "30" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 2" } ], "title": [ { "name": "text", "data": "(a)Preparation of Eu-PAAD hydrogel " }, { "name": "italic", "data": [ { "name": "text", "data": "via" } ] }, { "name": "text", "data": " Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": " complexation. (b)Fluorescence spectra of PAAD and Eu-PAAD hydrogels. Inset photos were taken under 365 nm UV light. (c)The proposed multistate fluorescence switching mechanism of Eu-PAAD hydrogel at different temperatures. (d)3D anticounterfeiting platform for on-demand decryption, which was prepared by folding 2D information carrier into 3D shape by hands and then immersed into Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": " solutions to fix such 3D structures. Different information would appear at 15 ℃(nothing), 40 ℃ (“木”), and 70 ℃(“村”). But the whole information(“树”) cannot be encoded unless EDTA is used to induce shape recovery from 3D to 2D" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "30", "type": "bibr", "rid": "R30", "data": [ { "name": "text", "data": "30" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019470&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019505&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019503&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "利用以上原理，作者设计了如" }, { "name": "xref", "data": { "text": "图2(d)", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2(d)" } ] } }, { "name": "text", "data": "所示2D蝴蝶形防伪水凝胶，将其折叠成3D形状，浸泡到Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "水溶液中固定形状，如此，事先设计好的信息被成功加密成3D蝴蝶形状的水凝胶结构。低温下，由于Eu-PAAD水凝胶强的AIE蓝色发光具有遮挡作用，这些用各种颜色的发光染料书写成的信息在紫外灯照射下无法被读取。当温度升高到40 ℃时，部分信息(“木”)可以被显示出来；而70 ℃时，显示出更多的信息(“村”)；只有使用乙二胺四乙酸二钠盐(EDTA)破坏Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "-AAc之间的配位键时，水凝胶的形状从3D恢复为2D后，完整信息(“树”)才被解密。由于加密过程中增加了形状记忆性质，将加密平台从2D提升至3D，信息安全性进一步得到提高。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "刺激响应及抗裂变水凝胶的仿生研究具有非常重要的学术价值和实际应用意义。然而，由于缺乏介观尺度的可视化手段，关于水凝胶韧性的机理研究明显不足，导致韧性水凝胶的合理设计具有非常大的挑战。2021年，唐本忠教授和Marcellan教授等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "31", "type": "bibr", "rid": "R31", "data": [ { "name": "text", "data": "31" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": " 设计合成了一种水溶性AIE分子TVPA，如" }, { "name": "xref", "data": { "text": "图3(a)", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3(a)" } ] } }, { "name": "text", "data": "所示。TVPA在聚集态具有较强的荧光(" }, { "name": "xref", "data": { "text": "图3(b)", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3(b)" } ] } }, { "name": "text", "data": ")，并且对所处环境的极性非常敏感，可通过共价键合引入到聚合物凝胶中，用于探测凝胶中的亲水疏水转变以及微观相分离。通过TVPA、N,N-二甲基丙烯酰胺(DMA,D)和N-异丙基丙烯酰胺(NIPAM,N)的自由基共聚反应，他们制备了强机械性能的热响应性水凝胶。所得共聚物网状结构在热刺激条件下，会从室温下的初始均一相转化为最低临界溶液温度(LCST," }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "c" } ] }, { "name": "text", "data": "=32 ℃)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "32", "type": "bibr", "rid": "R32", "data": [ { "name": "text", "data": "32" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "以上的两相态，并在温度降低到LCST以下时，可逆转化回初始的均一态。也就是说，温度高于LCST时，含有充足水分的PNIPAM链将经历从无规线团到蜷缩球体的转变(" }, { "name": "xref", "data": { "text": "图3(c)", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3(c)" } ] } }, { "name": "text", "data": ")，并坍塌成富含PNIPAM的疏水区域。同时，释放出的水分子被亲水性的PDMA相吸收，使得凝胶宏观尺度上拥有收缩(溶胀)能力。与此同时，共价键合在凝胶中的TVPA分子产生发光颜色和强度的双重变化，由亲水性PNIPAM链中的弱红色发光，转变为拥挤的PNIPAM疏水区域中的强蓝色发光。根据所用PDMA和NIPAM的质量比不同，得到了三种水凝胶GN2D3、GN3D3和GN6D3。如" }, { "name": "xref", "data": { "text": "图3(d)", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3(d)" } ] } }, { "name": "text", "data": "所示，三种水凝胶的荧光光谱在LCST附近都表现出明显的颜色和强度变化，表明TVPA可以作为凝胶中微环境变化的一种简单有效的报告分子。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "(a)TVPA探针的化学结构。(b)TVPA在水(10 μmol·L" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": ")、粘性甘油(10 μmol·L" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": ")中和固态的荧光光谱，插图为TVPA的荧光照片和量子产率(QY)。(c)水凝胶的设计原理及其在水溶液中亲-疏水转变过程示意图；以MBA作为交联剂，通过NIPAM、TVPA、PDMA单体的自由基聚合将TVPA引入到NIPAM交联聚合物网络中。根据NIPAM和PDMA的不同质量分数制备了三种水凝胶。在相转变温度(" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "c" } ] }, { "name": "text", "data": ")之上，PNIPAM聚合物网络坍塌，其疏水PNIPAM区域的TVPA的荧光强度增强，并发生蓝移现象。(d)GND水凝胶20 ℃和60 ℃下的荧光光谱(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " = 380 nm)，插图：GND水凝胶在20 ℃和60 ℃下的荧光照片。荧光显微镜下GN3D3热响应水凝胶制备状态下(e)和浸泡在60 ℃的水中(f)的荧光照片" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "31", "type": "bibr", "rid": "R31", "data": [ { "name": "text", "data": "31" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 3" } ], "title": [ { "name": "text", "data": "(a)Chemical structure of TVPA. (b)PL spectra of TVPA in water(10 μmol·L" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "), viscous glycerol(10 μmol·L" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "), and the solid state. Inset: the corresponding fluorescent photographs and quantum yield(QY) of TVPA. (c)Schematic illustration of design principle of hydrophilicity-hydrophobicity transformation in aqueous medium. TVPA was incorpor-ated into the crosslinked NIPAM polymer network by free radical polymerization of NIPAM, TVPA, PDMA macromonomer, and MBA crosslinker. The collapse of the resulting PNIPAM network is induced above its transition temperature(" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "c" } ] }, { "name": "text", "data": ") and the emission of the incorporated TVPA is expected to be enhanced and blue-shifted in the crowded and hydrophobic PNIPAM domains. Three hydrogels were prepared with different weight fractions of NIPAM and PDMA. (d)PL spectra of TVPA-incorporated GND hydrogels at 20 ℃ and 60 ℃ in water(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "=380 nm). Inset: fluorescent photos of GND hydrogels at 20 ℃ and 60 ℃ taken under 365 nm UV light. Fluorescent image of GN3D3 thermoresponsive hydrogel by fluorescent microscopy: (e)in the preparation state, (f)after immersing in water at 60 ℃" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "31", "type": "bibr", "rid": "R31", "data": [ { "name": "text", "data": "31" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019507&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019497&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019508&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "基于以上结果，作者利用荧光显微镜系统研究了水凝胶在介观尺度下的热响应形态学，观察到了GND水凝胶的热响应发射和形态变化过程。如" }, { "name": "xref", "data": { "text": "图3(e)~(f)", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3(e)~(f)" } ] } }, { "name": "text", "data": "所示，当温度为20 ℃时，水凝胶GN3D3呈现橙色；在60 ℃的水中浸泡30 min后，其荧光颜色则转变为蓝色，与宏观观测结果完全一致。条纹状牛顿环的出现说明光干涉的存在，据此作者提出干涉条纹的数量与相应物质的实际大小正相关，两个相邻同色条纹间的距离取决于该区域聚合物的折射率。在超过LCST的温度下，由于疏水性的聚合物和亲水性聚合物或水之间产生相分离，导致两相间折射率的巨大差异，因此，在" }, { "name": "xref", "data": { "text": "图3(f)", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3(f)" } ] } }, { "name": "text", "data": "中 Ⅰ 区呈现出强发射的球形区域。而高亲水性PDMA区域由于与水的折射率相近，使得 Ⅱ 区呈现出均匀的弱发光。这表明利用AIE技术不仅能够为刺激响应性水凝胶形貌变化提供简单、高对比度和原位可视化检测，也可以对组分依赖的相分离图案进行区分。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.1.2" } ], "title": [ { "name": "text", "data": "光刺激响应型AIE水凝胶" } ], "level": "3", "id": "s2a2" } }, { "name": "p", "data": [ { "name": "text", "data": "光作为一种有效的刺激手段，具有非侵入性和可控的优点。而光响应分子结构中通常含有能吸收光的官能团，在光照下会发生某些化学或物理反应，产生一系列结构和形态的变化，从而表现出特定的功能。光响应聚合物凝胶由于其出色的柔性和强度，在药物输送、摄影、颜料/涂料、传感器及组织再生等领域具有广泛的实际应用价值。然而，目前大多数光响应聚合物凝胶是不发光的。荧光是肉眼可见的最灵敏的检测信号之一，将荧光材料引入光响应聚合物凝胶体系对其在刺激响应光学存储器、可检测药物输送体系、化学/生物传感器及生物成像等领域的应用非常重要且存在巨大的挑战。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "首尔大学Park等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "R33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "分别选择Z-2,3-二(4-(4-吡啶基)苯基)丙烯腈(Py-CN-MBE)和聚丙烯酸(PAA)作为超分子交联剂和聚合物基体，设计了如" }, { "name": "xref", "data": { "text": "图4(a)", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4(a)" } ] } }, { "name": "text", "data": "所示的具有强荧光的Py-CN-MBE/PAA光响应聚合物凝胶。Py-CN-MBE以反式异构体形式，通过吡啶单元与PAA上羧基形成多重氢键，发生交联，如" }, { "name": "xref", "data": { "text": "图4(b)", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4(b)" } ] } }, { "name": "text", "data": "所示。Py-CN-MBE通过π-π相互作用紧密堆积在PAA聚合物基体中，发出强烈的绿色荧光。在紫外(UV)照射下，Py-CN-MBE发生光异构化，形成大量顺式异构体，这些异构体不能与PAA形成稳定的氢键。因此，凝胶转化为溶胶，同时发出较弱的蓝色荧光。这种具有强荧光的光响应聚合物凝胶体系有望用于药物输送、摄影、颜料/涂料、光学存储、生物医学成像及生物传感器等领域。" } ] }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "(a)Py-CN-MBE和PAA的化学结构；(b)聚合物光异构化诱导荧光开关策略示意图；(c)乙醇中透明凝胶(左)以及紫外光诱导转变为溶液(右)后分别在日光和紫外光照射下的照片" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "R33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 4" } ], "title": [ { "name": "text", "data": "(a)Chemical structures of Py-CN-MBE and PAA molecules. (b)Strategy of photoisomerizaton-induced fluorescence switching in polymer. (c)Photo images of the transparent gel(left) in ethanol and photo images of the photoinduced solution(right) under room light and UV light" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "R33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019499&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019533&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019517&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2019年，吉林大学姜世梅课题组" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "34", "type": "bibr", "rid": "R34", "data": [ { "name": "text", "data": "34" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "设计合成了氰基苯乙烯修饰的均苯三甲酰胺(BTA)胶凝剂BTTPA，如" }, { "name": "xref", "data": { "text": "图5(a)", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5(a)" } ] } }, { "name": "text", "data": "所示。BTA中三个酰胺键连接在同一个中心苯环上，这种特殊的结构在构建层级超分子结构中具有巨大的优势。这三个酰胺键不仅可以提供较强的三重氢键，而且也可以提供一维生长趋向。氰基苯乙烯π-共轭骨架具有AIE活性，并且可产生光异构化现象，对聚集行为非常敏感。通过氢键和π-π相互作用的协同效应，胶凝剂BTTPA可形成有序的自组装，从而影响π-共轭的氰基苯乙烯的堆积方式，形成具有特异性发光行为的凝胶。BTTPA可以在不同水体积含量的二甲基亚砜(DMSO)和水的混合溶剂中形成两种凝胶。当水含量为15%时，BTTPA形成黄色凝胶(G-gel)；当水含量上升为30%~50% 时，BTTPA形成白色凝胶(B-gel)。高含水量时，BTTPA可以通过与水分子形成的N—H…O和O—H…O氢键稳定二聚体结构，形成重叠构型；而低水含量时，不能够形成足够的氢键来支持这种重叠构型(Overlapped structure)，因此BTTPA更倾向于形成滑移构型(Slipped structure)(" }, { "name": "xref", "data": { "text": "图5(b)", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5(b)" } ] } }, { "name": "text", "data": "示意图)。由于两种凝胶堆积方式不同，导致其聚集诱导发光增强(AIEE)特性不同，G-gel发出绿色荧光，B-gel发出蓝色荧光。" } ] }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "(a)BTTPA分子的化学结构；(b)BTTPA在G-gel和B-gel中可能的自组装行为示意图及其在紫外灯下的荧光照片；(c)G-gel在紫外灯照射前后的照片；(d)荧光光谱(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " = 345 nm);(e)紫外-可见吸收光谱；(f)由G-gel(角落)和B-gel(中心)制成的光诱导保密图案照片" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "34", "type": "bibr", "rid": "R34", "data": [ { "name": "text", "data": "34" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 5" } ], "title": [ { "name": "text", "data": "(a)Chemical structure of BTTPA molecule. (b)Proposed illustration of the self-assembly behaviors of BTTPA in G-gel and B-gel. (c)Photographs of G-gel before and after UV irradiation. (d)Fluorescence spectra(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " = 345 nm). (e)UV-Vis absorption spectra. (f)Photographs of a photoinduced confidentiality pattern made from G-gel(at the corner) and B-gel(in the center)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "34", "type": "bibr", "rid": "R34", "data": [ { "name": "text", "data": "34" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019537&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019541&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019525&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "通常情况下，氰基苯乙烯衍生物在聚集态的堆积非常紧密，紫外光照射后也非常稳定，不会发生光异构化现象。然而，这一工作中获得的两种凝胶分别表现出不同的光响应行为。紫外光照射时，G-gel塌陷并迅速转变为粘性溶胶(" }, { "name": "xref", "data": { "text": "图5(c)~(e)", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5(c)~(e)" } ] } }, { "name": "text", "data": ")，但是，B-gel在紫外光照射下没有明显变化。说明G-gel发生了光异构化，而B-gel没有发生光异构化。由于光异构化的发生取决于分子所处的空间大小，而这个空间大小受分子排列的直接影响。G-gel的结构较松散，为光异构化的发生提供了足够的空间。相比较而言，B-gel呈现更加紧密的六角形堆积结构，限制了分子的自由转动，使得氰基苯乙烯不能发生构型变化。因此，B-gel表现出优异的光稳定性，而G-gel表现出优异的光敏性。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "利用这两种凝胶的不同光响应行为，该课题组开发了一种图形化的光诱导保密模式。" }, { "name": "xref", "data": { "text": "图5(f)", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5(f)" } ] } }, { "name": "text", "data": "所示的包含五个圆圈的图形中，边上的四个圆圈装有G-gel，中心的圆圈装有B-gel。五个圆圈的绿色或蓝色荧光在紫外灯下均清晰可见，当用紫外灯照射一定时间后，绿色荧光部分逐渐减弱，但蓝色荧光部分亮度保持不变，因此仅中心的圆圈是清晰可见的。这项工作为开发新型智能材料开辟了新的途径。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.2" } ], "title": [ { "name": "text", "data": "化学因素" } ], "level": "2", "id": "s2b" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.2.1" } ], "title": [ { "name": "text", "data": "pH值刺激响应型AIE水凝胶" } ], "level": "3", "id": "s2b1" } }, { "name": "p", "data": [ { "name": "text", "data": "pH响应材料是指结构和性能会随着体系中氢离子浓度变化而发生改变的材料。pH 响应材料的分子结构中主要包含以下两类官能团。第一类为胺基、吡啶、咪唑等碱性基团，当pH 发生改变时，这类基团的离子化状态发生改变，引起其分子结构在水中的溶解性发生变化。一般而言，含有这类基团的聚合物在中性或碱性条件下不溶于水；在酸性条件下，碱性基团会发生质子化而带有正电荷，故而呈现出极性，使聚合物可溶于水。第二类是腙键、乙二缩醛键、羧酸酰胺键、原酸酯键等在酸性条件下不稳定的化学键，这些化学键在弱酸性条件下就能够快速水解，从而引起分子结构及其亲疏水性的改变。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "与正常组织周围的中性pH(~7.4)相比，肿瘤组织周围往往呈现弱酸性(pH" }, { "name": "text", "data": "<" }, { "name": "text", "data": "6.5)，成为区分鉴别肿瘤的重要特征。2016年，吉林大学林权课题组与长春工业大学杨旭东课题组" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "35", "type": "bibr", "rid": "R35", "data": [ { "name": "text", "data": "35" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "设计合成了一种具有核壳结构的水凝胶纳米颗粒，具有对pH和温度双重响应特征，并且具有双发射。这种水凝胶纳米颗粒的核由稀土配合物Eu(Ⅲ)-(TTA)" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "Phen掺杂的聚(N-异丙基丙烯酰胺)-共-聚苯乙烯(PNIPAM-co-PS)构成，壳结构由AIE分子d-TPE掺杂的聚(N-异丙基丙烯酰胺)-共-聚丙烯酸(PNIPAM-co-PAA)构成，如" }, { "name": "xref", "data": { "text": "图6(a)", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6(a)" } ] } }, { "name": "text", "data": "所示。该水凝胶纳米颗粒的疏水性中心核可发出铕配合物的特征红色荧光，并且这种红色荧光不随pH的变化而改变；而其亲水性的外壳可以发出AIE分子的特征蓝色荧光，并且这种蓝色荧光具有pH响应能力(" }, { "name": "xref", "data": { "text": "图6(b)", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6(b)" } ] } }, { "name": "text", "data": ")。同时，蓝色发光和红色发光都具有温度响应能力。这种双发射的水凝胶纳米颗粒可以非常灵敏地检测癌细胞(" }, { "name": "xref", "data": { "text": "图6(c)、(d)", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6(c)、(d)" } ] } }, { "name": "text", "data": ")，并且可用于发光纳米凝胶测温或生物成像，在癌症诊断领域激发了更多的研究。" } ] }, { "name": "fig", "data": { "id": "F6", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图6" } ], "title": [ { "name": "text", "data": "(a)d-TPE的化学结构以及核/壳型水凝胶纳米粒子的组装示意图；(b)水凝胶纳米颗粒水溶液在不同pH值(5.0,6.0,7.0,7.4)的荧光颜色和荧光光谱；注射2 d后解剖荷瘤小鼠正常组织(c)和肿瘤组织(d)的共聚焦荧光图像" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "35", "type": "bibr", "rid": "R35", "data": [ { "name": "text", "data": "35" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 6" } ], "title": [ { "name": "text", "data": "(a)Chemical structure of d-TPE and assembly diagram of core/shell hydrogel nanoparticles. (b)Fluorescence color and PL spectra of the hydrogel nanoparticle aqueous solution at different pH values(5.0, 6.0, 7.0, 7.4). Confocal fluorescence images of dissected normal tissue(c) and tumor tissue(d) of tumor-bearing mice sacrificed at 2 d post injection" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "35", "type": "bibr", "rid": "R35", "data": [ { "name": "text", "data": "35" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019529&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019549&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019532&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "目前pH值刺激响应型AIE水凝胶的响应方式大多为发光颜色或者发光亮度的变化，然而，要实现在单一刺激下发光颜色、亮度和凝胶形状同时发生变化仍是一项不小的挑战。2019年，唐本忠教授课题组" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "36", "type": "bibr", "rid": "R36", "data": [ { "name": "text", "data": "36" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "成功制备了一种单一pH刺激下就能同时实现荧光颜色、亮度以及3D形状变化的仿生水凝胶。如" }, { "name": "xref", "data": { "text": "图7(a)", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7(a)" } ] } }, { "name": "text", "data": "所示，该双层水凝胶采用离子交联聚合物聚丙烯酰胺-r-4-苯乙烯磺酸钠(PAS)作为活性层和钝化层的基质，以具有pH响应特性的AIE分子四-(4-吡啶苯基)乙烯(TPE-4Py)为活性层的核心功能元件。中性pH时，TPE-4Py具有疏水性，分子聚集，呈现出宝石蓝色的发光。当pH降低时，TPE-4Py被质子化，生成带有正电荷的4H-TPE-4Py" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "，发光红移，变为黄色发光。质子化同时提高了AIE分子的水溶性，使得其聚集程度降低，分子内旋转加剧，导致发光减弱。与此同时，带正电荷的4H-TPE-4Py" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "与被动层PAS中带负电荷的磺酸基团发生静电相互作用，4H-TPE-4Py" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "作为额外的物理交联点，导致主动层收缩，水凝胶逐渐变形。变形过程中，由于4H-TPE-4Py" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "与离子交联聚合物网络中的聚合链发生静电相互作用，其分子内旋转受限，从而黄色荧光亮度增强。基于此，将这种双层水凝胶剪成花瓣形状，在酸性环境中可同时实现颜色、亮度和形状的变化行为(" }, { "name": "xref", "data": { "text": "图7(b)", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7(b)" } ] } }, { "name": "text", "data": ")。该类水凝胶有望用于3D/4D打印、柔性机器人及智能可穿戴设备等领域。" } ] }, { "name": "fig", "data": { "id": "F7", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图7" } ], "title": [ { "name": "text", "data": "(a)AIE双层水凝胶驱动器结构及其荧光颜色、强度和形状同时变化的机制示意图；(b)在365 nm紫外光照射下拍摄的花瓣样水凝胶驱动器颜色和形状同步变化图(上为平视图，下为俯视图),pH=3.12" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "36", "type": "bibr", "rid": "R36", "data": [ { "name": "text", "data": "36" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 7" } ], "title": [ { "name": "text", "data": "(a)Schematic illustration of simultaneous changes in fluorescent color and brightness and shape of a AIE bilayer hydrogel actuator and the mechanism involved. (b)Simultaneous emission change and complex shape deformation of hydrogel actuator(Photographs were taken under 365 nm UV illumination. The upper line is flat view and the lower line is plane view), pH=3.12" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "36", "type": "bibr", "rid": "R36", "data": [ { "name": "text", "data": "36" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019552&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019570&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019567&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "圆偏振发光(CPL)是指手性发光体系发射出具有差异的左旋和右旋圆偏振光的现象" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "37", "type": "bibr", "rid": "R37", "data": [ { "name": "text", "data": "37" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。CPL反映的是手性发光体系的激发态结构信息，在立体显示、信息存储与处理、CPL 激光、生物探针、光催化不对称合成等领域具有广泛的应用前景" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "38", "type": "bibr", "rid": "R38", "data": [ { "name": "text", "data": "38" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "39", "type": "bibr", "rid": "R39", "data": [ { "name": "text", "data": "39" } ] } } ], "rid": [ "R38", "R39" ], "text": "38-39", "type": "bibr" } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。但是这些应用往往要求CPL材料具有较大的发光不对称因子(" }, { "name": "italic", "data": [ { "name": "text", "data": "g" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "lum" } ] }, { "name": "text", "data": ")和多色可调特性。人们通常采用超分子自组装、能量转移及掺杂液晶等方法来放大发光不对称因子" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "40", "type": "bibr", "rid": "R40", "data": [ { "name": "text", "data": "40" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。为了获得多色CPL，常用的方法是使用几种发光颜色不同的手性化合物，但是这种方法涉及复杂冗繁的有机合成过程。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2019年，吉林大学姜世梅教授课题组" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "41", "type": "bibr", "rid": "R41", "data": [ { "name": "text", "data": "41" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "设计了一种单分子体系Chol-CN-Py，在聚集态下同时获得了较大的发光不对称因子和颜色可控CPL。如" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "所示，Chol-CN-Py单分子体系包含一个吡啶修饰的氰基苯乙烯结构、一个手性胆固醇基团和一个起连接作用的酯键。其中，氰基苯乙烯作为非手性AIE荧光分子，可在凝聚态发出强荧光；胆固醇部分在单体状态下的弱手性可在聚集后被放大并传递给非手性的AIE发光团，产生聚集诱导圆二色性(AICD)和聚集诱导圆偏振发光(AICPL)。另外，吡啶作为碱性基团可被质子化，质子化后能级发生相应的变化，从而在单一分子体系中实现颜色可调的CPL。结果表明，Chol-CN-Py成胶能力强，可形成明显的纳米螺旋结构，在凝胶和干凝胶薄膜两种形态下发出明亮的蓝色荧光。三氟乙酸刺激后，干凝胶薄膜的发光波长发生明显红移。并且，干凝胶薄膜态中手性结构和手性传递在质子化的过程中也得以保留。如" }, { "name": "xref", "data": { "text": "图8(f)", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8(f)" } ] } }, { "name": "text", "data": "所示，通过控制质子化的程度，干凝胶薄膜呈现出明显的CPL信号，从480 nm红移到530 nm，颜色由蓝色、经绿色和黄色最终变为橙色，并且整个过程中的不对称性和" }, { "name": "italic", "data": [ { "name": "text", "data": "g" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "lum" } ] }, { "name": "text", "data": "值保持不变。这项工作为在单一体系中开发新型智能 CPL 可调控材料提供了新的视角。" } ] }, { "name": "fig", "data": { "id": "F8", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图8" } ], "title": [ { "name": "text", "data": "(a)Chol-CN-Py的化学结构；(b)Chol-CN-Py凝胶在DMSO中成胶时485 nm处的动态荧光强度，插图：溶胶状态和凝胶状态下的的荧光光谱(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "=410 nm)及其在紫外光下的荧光图像；(c)Chol-CN-Py凝胶的CPL光谱(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "=370 nm);(d)干凝胶的扫描电镜图；(e)298 K下，不同浓度TFA处理10 s后干凝胶薄膜的归一化荧光光谱(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "=410 nm);(f)干凝胶薄膜质子化后的CPL光谱；(g)干凝胶薄膜质子化后的" }, { "name": "italic", "data": [ { "name": "text", "data": "g" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "lum" } ] }, { "name": "text", "data": "图；(h)干凝胶薄膜暴露在不同浓度TFA下的多色CPL图" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "41", "type": "bibr", "rid": "R41", "data": [ { "name": "text", "data": "41" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 8" } ], "title": [ { "name": "text", "data": "(a)Chemical structure of Chol-CN-Py. (b)Dynamic fluorescence intensity of the Chol-CNPy gel in DMSO undergoing gelation at 485 nm. Inset: the hot solution and gel fluorescence spectra(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "=410 nm) and fluorescence image under UV light. (c)CPL spectra of the Chol-CN-Py gel(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "=370 nm). (d) SEM image of xerogel. (e)Normalized fluorescence spectra of xerogel films treated with different concentrations of TFA at 298 K for 10 s(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "=410 nm). (f)CPL spectra upon protonation(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "=370 nm). (g)" }, { "name": "italic", "data": [ { "name": "text", "data": "g" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "lum" } ] }, { "name": "text", "data": " of xerogel films upon protonation. (h)Multi-color CPL upon exposure of the xerogel films to different amount of TFA" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "41", "type": "bibr", "rid": "R41", "data": [ { "name": "text", "data": "41" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019573&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019577&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019578&type=" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.2.2" } ], "title": [ { "name": "text", "data": "溶剂刺激响应型AIE水凝胶" } ], "level": "3", "id": "s2b2" } }, { "name": "p", "data": [ { "name": "text", "data": "除了pH刺激因素外，还有其他外界刺激因素，如溶剂等都会对凝胶的性质产生一定影响。长期以来，人们受到自然界中生物的启发，发明了飞机、潜艇、雷达等，这些发明促进了社会的发展。近期，中科院宁波材料所智能高分子材料团队陈涛研究员和路伟研究员" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "42", "type": "bibr", "rid": "R42", "data": [ { "name": "text", "data": "42" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "受到章鱼的启发，设计研发了一个章鱼样的形状/颜色可协同变化并且可以定向游泳运动的驱动器。受经典有机AIE分子设计的启发，他们将传统碳点(CDs)表面用乙烯基功能化，获得表面带有可旋转疏水基团的乙烯基VCDs)。然后通过丙烯酰胺(AAm)、丙烯酸(AAc)和 VCDs 的自由基共聚反应制备了发蓝色荧光的乙二醇VCDs聚合物凝胶。将其作为主动层，3M VHB弹性体作为钝化层，组合制备成各项异性双层驱动器。当驱动器浸入水溶液中时，聚合物凝胶层会吸水，诱导疏水性 VCDs 簇的形成，发光从蓝色变为聚集体的红色发光(" }, { "name": "xref", "data": { "text": "图9(a)~(b)", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9(a)~(b)" } ] } }, { "name": "text", "data": ")。除了蓝色到红色的发射颜色变化之外，聚合物凝胶层吸水后会膨胀，促使双层驱动器依其几何图形变形为各种3D结构。重要的是，水-乙二醇交换过程还伴随着通过马兰戈尼效应产生的表面张力梯度，从而促进驱动器产生自主的游泳运动。该团队利用这种双层驱动器模拟了绣球花春夏交替或生长的土壤pH从酸性变为碱性过程中花瓣颜色从蓝色变为红色的过程。如" }, { "name": "xref", "data": { "text": "图9(c)", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9(c)" } ] } }, { "name": "text", "data": "所示，用这种人工智能材料做成的花朵可以在水的刺激下逐渐盛开，并产生蓝色到红色的颜色变化。" } ] }, { "name": "fig", "data": { "id": "F9", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图9" } ], "title": [ { "name": "text", "data": "(a)双层乙二醇VCDs聚合物/3M VHB水凝胶驱动器在水中时，形状和荧光颜色同步变化机理示意图；(b)VCDs聚合物凝胶的化学结构及其可逆双开关模式荧光(蓝色分散荧光和红色AIE)示意图；(c)绣球花开花同时发生蓝-红颜色变化过程示意图以及在365 nm紫外光照射下拍摄的用聚合物凝胶制成的人工绣球花同时展示开花和发生蓝-红颜色变化的相应图片；(d)~(e)基于VCDs聚合物凝胶的人造章鱼软机器人的形状和颜色协同变化以及定向泳动的示意图和照片" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "42", "type": "bibr", "rid": "R42", "data": [ { "name": "text", "data": "42" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 9" } ], "title": [ { "name": "text", "data": "(a)Schematic illustration of the synergistic shape and fluorescence color changes of the bilayer glycol VCDs polymer gel/3M VHB actuator in water and the involved mechanism. (b)Chemical structure of the VCDs polymer gel and schematic representation of the reversible two-switch-mode fluorescence(blue dispersed fluorescence and red AIE). (c)Schemes representing the simultaneous blooming and blue-to-red color change process of Hydrangea Bush, as well as the corresponding photos of polymer gel-based artificial Hydrangea Bush that display simultaneous blooming and color-changing behaviors. Photos were taken under 365 nm UV illumination(8 W). (d)-(e)Photos and schemes showing the synergistic shape/color change and directional swimming locomotion of the VCDs polymer gel-based artificial octopus-like soft robot" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "42", "type": "bibr", "rid": "R42", "data": [ { "name": "text", "data": "42" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019585&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019587&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019600&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "在此基础上，团队进一步设计了第一个可协同变形、变色和定向运动的章鱼样凝胶机器人。如" }, { "name": "xref", "data": { "text": "图9(d)", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9(d)" } ] } }, { "name": "text", "data": "所示，采用八个乙二醇 VCDs 凝胶双层驱动器作为“章鱼爪子”，一个单一乙二醇 VCDs 凝胶作为“章鱼头”。最初，这个章鱼样凝胶机器人的爪子部分呈现深蓝色，在水面上时，八个爪子的乙二醇VCDs 凝胶层开始吸水并促使这些爪子弯曲，并且伴随蓝色到红色的颜色变化。同时，头部的乙二醇VCDs凝胶层“挤出”乙二醇，使其表面产生张力梯度，推动章鱼样机器人沿着虽曲折但定向的轨迹游动。类似地，这种凝胶章鱼的协同颜色和形状变化也可以通过将其浸入乙二醇中来可逆进行。这种三功能协同作用的 VCDs 凝胶游动驱动器充分展示了仿生智能变色软机器人的可能性，有望用于环境、水上探测和伪装等领域。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.2.3" } ], "title": [ { "name": "text", "data": "离子刺激响应型AIE水凝胶" } ], "level": "3", "id": "s2b3" } }, { "name": "p", "data": [ { "name": "text", "data": "离子对于维持人体内生理环境的稳定起着重要作用。离子响应型水凝胶作为新型智能材料，在化学传感、信息加密等领域有潜在应用价值。近年来，超分子化学的快速发展为构建新型水凝胶材料提供了新契机。超分子聚合物水凝胶因含水量高" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "43", "type": "bibr", "rid": "R43", "data": [ { "name": "text", "data": "43" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、非共价相互作用丰富" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "44", "type": "bibr", "rid": "R44", "data": [ { "name": "text", "data": "44" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "45", "type": "bibr", "rid": "R45", "data": [ { "name": "text", "data": "45" } ] } } ], "rid": [ "R44", "R45" ], "text": "44-45", "type": "bibr" } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "等优点得到了广泛研究。具有AIE效应的刺激响应型超分子聚合物水凝胶不仅表现出源自非共价键的动力学特征，而且还表现出对各种外界刺激的荧光响应。因此，超分子聚合物是构建刺激响应型AIE水凝胶功能材料的理想平台之一。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2019年，西北师范大学林奇、张有明等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "46", "type": "bibr", "rid": "R46", "data": [ { "name": "text", "data": "46" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "利用萘酰亚胺衍生物(M)和三-(4-吡啶基)-均苯三甲酰胺(Q)在二甲基亚砜(DMSO)与水体积比为6∶4的溶液中，成功制备了如" }, { "name": "xref", "data": { "text": "图10(a)", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10(a)" } ] } }, { "name": "text", "data": "所示的新型AIE双组分超分子水凝胶MQ-G。其中M中的萘酰亚胺基团可作为π-π相互作用位点和荧光发色团。M中的萘也可充当π电子给体与Q中的电子受体吡啶基团形成给受体相互作用。此外，Q中的三脚架型酰胺基团在自组装过程中可形成多重氢键。因此，MQ-G水凝胶具有较强的稳定性。如" }, { "name": "xref", "data": { "text": "图10(b)", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10(b)" } ] } }, { "name": "text", "data": "所示，MQ在含水量达到40%的DMSO/水混合溶液中可形成稳定的双组分超分子水凝胶MQ-G，并发出较强的荧光。当含水量大于40%时，MQ-G逐渐变得不稳定，荧光强度减弱。" } ] }, { "name": "fig", "data": { "id": "F10", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图10" } ], "title": [ { "name": "text", "data": "(a)M和Q的化学结构式以及水凝胶MQ-G可能的自组装和离子识别机制；(b)MQ在不同水含量的溶液中时在365 nm紫外灯下的荧光照片；(c)水凝胶MQ-G中加入不同阳离子后在紫外光或自然光下的响应情况；(d)水凝胶MQ-G和Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "复合物中加入不同阴离子后在紫外光或自然光下的响应情况；(e)水凝胶MQ-G薄膜对Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "的检测照片；(f)水凝胶MQ-G+Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "薄膜对H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "P " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019605&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019623&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019591&type=" } } } ] }, { "name": "text", "data": "的检测照片" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "46", "type": "bibr", "rid": "R46", "data": [ { "name": "text", "data": "46" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 10" } ], "title": [ { "name": "text", "data": "(a)Chemical structures of M and Q and the proposed assembly and recognition mechanism of the MQ-G. (b)Photographs of the MQ solutions containing different water contents under the UV lamp(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "=365 nm). Fluorescent and natural light responses of the bi-component hydrogel MQ-G upon adding of various cations(c) and the metal hydrogel MQ-G+Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": " upon adding of various anions(d). (e)Photos of the MQ-G based thin film fluorescently detect Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": " in aqueous solution. (f)Photos of the MQ-G + Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": " based metal thin film fluorescently detect H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "P " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019626&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019614&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019612&type=" } } } ] }, { "name": "text", "data": " in aqueous solution, illuminated at 365 nm" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "46", "type": "bibr", "rid": "R46", "data": [ { "name": "text", "data": "46" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019632&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019621&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019618&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "MQ-G水凝胶具有离子响应功能，可以灵敏地检测水中的Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "和H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "P " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019639&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019644&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019637&type=" } } } ] }, { "name": "text", "data": "。如" }, { "name": "xref", "data": { "text": "图10(c)", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10(c)" } ] } }, { "name": "text", "data": "所示，将Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "水溶液(浓度为 0.1 mol·L" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": ")加入到MQ-G水凝胶中，MQ-G的橙色荧光发生猝灭，而其他阳离子(如Mg" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Pb" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Cr" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "、Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "、Co" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Ni" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Cu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Ag" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "、Zn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "等)未引起类似的荧光变化。因此，MQ-G可以选择性地检测水中的Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "。检测过程中生成的金属水凝胶(MQ-G+Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": ")还可以进一步用于阴离子的检测。如" }, { "name": "xref", "data": { "text": "图10(d)", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10(d)" } ] } }, { "name": "text", "data": "所示，在365 nm紫外光照射下，只有H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "P" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019646&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019652&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019658&type=" } } } ] }, { "name": "text", "data": "能使MQ-G + Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "水凝胶发出橙色荧光。其他阴离子未能达到相同效果。因此，MQ-G+Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "水凝胶可以选择性地用于水中H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "P" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019660&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019670&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019669&type=" } } } ] }, { "name": "text", "data": "的荧光检测。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "受到以上研究结果的启发，该团队设计了可重复书写的超分子智能荧光显示材料。如" }, { "name": "xref", "data": { "text": "图10(f)", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10(f)" } ] } }, { "name": "text", "data": "所示，将MQ-G和MQ-G+Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "的热溶液倒在干净的玻璃表面，在空气中干燥后，分别获得了基于MQ-G和MQ-G+Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "的凝胶薄膜。用毛笔蘸取Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "水溶液在MQ-G凝胶薄膜上书写时，在365 nm紫外光照射下可观察到明显的荧光变化。当用毛笔蘸取H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "P " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019671&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019673&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019683&type=" } } } ] }, { "name": "text", "data": "水溶液在MQ-G+Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "薄膜上书写时，可以有效地恢复MQ-G的荧光。因此，这种基于MQ-G和MQ-G+Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "的凝胶薄膜材料不仅可以作为一种可逆检测Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "和H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "P" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019675&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019679&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019677&type=" } } } ] }, { "name": "text", "data": "的简便工具，也可以作为一种可擦除的安保荧光显示材料。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2021年，魏太保、林奇等进一步开发了白光发射的超分子聚合物AIE水凝胶NDG" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "47", "type": "bibr", "rid": "R47", "data": [ { "name": "text", "data": "47" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。如" }, { "name": "xref", "data": { "text": "图11(a)", "type": "fig", "rid": "F11", "data": [ { "name": "text", "data": "图11(a)" } ] } }, { "name": "text", "data": "所示，作者采用1-萘乙酰基修饰的三脚架型均苯酰肼(NTS)作为主体，三-(4-吡啶基)-均苯三甲酰胺(DTB)为客体，通过简单的主客体相互作用，NTS和DTB可以在DMSO/水(3.3∶6.7, " }, { "name": "italic", "data": [ { "name": "text", "data": "v" } ] }, { "name": "text", "data": "∶" }, { "name": "italic", "data": [ { "name": "text", "data": "v" } ] }, { "name": "text", "data": ")混合溶液中自组装成为稳定的超分子聚合物凝胶NDG，并发出较强的白色发光。NDG能够特异性检测Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "和F" }, { "name": "sup", "data": [ { "name": "text", "data": "-" } ] }, { "name": "text", "data": "，如" }, { "name": "xref", "data": { "text": "图11(b)", "type": "fig", "rid": "F11", "data": [ { "name": "text", "data": "图11(b)" } ] } }, { "name": "text", "data": "所示，检测限分别为5.33 nmol·L" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "和16.1 nmol·L" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "。NDG的干凝胶还可以吸附和分离Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "，吸附率为99.26%。基于NDG制备的凝胶薄膜也可以用作可反复书写的荧光显示材料，用于连续检测Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "和F" }, { "name": "sup", "data": [ { "name": "text", "data": "-" } ] }, { "name": "text", "data": "。这项工作为开发白光发光材料提供了新思路。" } ] }, { "name": "fig", "data": { "id": "F11", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图11" } ], "title": [ { "name": "text", "data": "(a)NTS和DTB的化学结构式以及水凝胶NDG可能的自组装和离子识别机制；(b)水凝胶NDG在Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "和F" }, { "name": "sup", "data": [ { "name": "text", "data": "-" } ] }, { "name": "text", "data": "响应前后的SEM以及荧光照片" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "47", "type": "bibr", "rid": "R47", "data": [ { "name": "text", "data": "47" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 11" } ], "title": [ { "name": "text", "data": "(a)Chemical structures of NTS and DTB and the proposed assembly and recognition mechanism of the NDG. (b)SEM and fluorescent photograph of NDG in the presence of Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": " and F" }, { "name": "sup", "data": [ { "name": "text", "data": "-[" }, { "name": "xref", "data": { "text": "47", "type": "bibr", "rid": "R47", "data": [ { "name": "text", "data": "47" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019689&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019692&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019682&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "除了上述萘酰胺衍生物之外，一些金属纳米簇也能够用于构筑AIE水凝胶。2019年，东南大学王雪梅教授课题组" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "48", "type": "bibr", "rid": "R48", "data": [ { "name": "text", "data": "48" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "利用二价金属离子诱导的纳米簇聚集开发了一种兼具AIE效应和AIECL(聚集诱导电化学发发光)效应的水凝胶体系。如" }, { "name": "xref", "data": { "text": "图12", "type": "fig", "rid": "F12", "data": [ { "name": "text", "data": "图12" } ] } }, { "name": "text", "data": "所示，该课题组利用Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "与磷酸基团之间的配位作用，诱导腺苷磷酸(AXP)包覆的金纳米簇发生聚集，形成类似羟基磷灰石结构的AIE水凝胶。并且，该AIE水凝胶的AIECL效应(50倍增强)比AIE 效应(5倍增强)更显著。该AIE水凝胶可用于检测Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "结合蛋白钙调素(Calmodulin)，检测限达0.1 mg/mL。鉴于二价金属离子在生命过程中的重要作用，这项工作有望为生物分子响应型AIECL活性水凝胶的设计提供新思路。" } ] }, { "name": "fig", "data": { "id": "F12", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图12" } ], "title": [ { "name": "text", "data": "二价阳离子(以Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "为例) 诱导具有钙调素调控电化学发光性质的金属纳米团簇聚集示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "48", "type": "bibr", "rid": "R48", "data": [ { "name": "text", "data": "48" } ] } }, { "name": "text", "data": "]" } ] } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 12" } ], "title": [ { "name": "text", "data": "Illustration of bivalent cations(Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " as an example) induced aggregation of metallic nanoclusters with calmodulin-regulated electrochemiluminescence" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "48", "type": "bibr", "rid": "R48", "data": [ { "name": "text", "data": "48" } ] } }, { "name": "text", "data": "]" } ] } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019695&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019714&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019696&type=" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.3" } ], "title": [ { "name": "text", "data": "生物因素" } ], "level": "2", "id": "s2c" } }, { "name": "p", "data": [ { "name": "text", "data": "酶响应型水凝胶材料作为一种新型智能材料，具有优异的生物性能而备受关注。ATP酶又称为三磷酸腺苷酶，能将三磷酸腺苷(ATP)催化水解为二磷酸腺苷(ADP)和磷酸根离子，并释放能量，广泛存在于各种生命活动中。2018年，黄飞鹤、吉晓帆等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "49", "type": "bibr", "rid": "R49", "data": [ { "name": "text", "data": "49" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "报道了一种ATP酶刺激响应AIE型超分子荧光水凝胶(3)。如" }, { "name": "xref", "data": { "text": "图13", "type": "fig", "rid": "F13", "data": [ { "name": "text", "data": "图13" } ] } }, { "name": "text", "data": "所示，该水凝胶利用聚苯乙烯磺酸钠(1)与含两个季铵盐阳离子的四苯乙烯衍生物(2)之间的静电相互作用，经自组装而成，这一过程导致四苯乙烯聚集，从而赋予该水凝胶AIE特性。向水凝胶体系中加入ATP时，由于ATP与四苯乙烯的静电相互作用强于四苯乙烯与聚苯乙烯磺酸钠之间的静电相互作用，因此水凝胶的网状结构被破坏，水凝胶向溶胶转变，四苯乙烯的聚集程度降低，荧光强度降低。随后，向该溶胶中加入ATP酶，ATP被分解，四苯乙烯与聚苯乙烯磺酸钠间的静电相互作用被重建，溶胶向凝胶转变，荧光增强。并且，该荧光超分子水凝胶可以跨越细胞膜进入细胞质，可应用于细胞成像(见" }, { "name": "xref", "data": { "text": "图13(b)", "type": "fig", "rid": "F13", "data": [ { "name": "text", "data": "图13(b)" } ] } }, { "name": "text", "data": ")。基于这些优点，该水凝胶有望用于细胞质中生物氧化过程的成像分析、药物递送等。" } ] }, { "name": "fig", "data": { "id": "F13", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图13" } ], "title": [ { "name": "text", "data": "(a)化合物1和2的化学结构式以及水凝胶3可能的自组装、ATP和酶响应机制；(b)水凝胶3与HEK cells孵化后的激光共聚焦显微成像照片(标尺为20 μm)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "49", "type": "bibr", "rid": "R49", "data": [ { "name": "text", "data": "49" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 13" } ], "title": [ { "name": "text", "data": "(a)Chemical structures of 1 and 2 and the proposed assembly and recognition mechanism of the hydrogel 3. (b)Confocal laser scanning microscopy images of HEK cells incubated with hydrogel 3(scale bar is 20 μm)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "49", "type": "bibr", "rid": "R49", "data": [ { "name": "text", "data": "49" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019704&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019721&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=28019707&type=" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "3" } ], "title": [ { "name": "text", "data": "结论与展望" } ], "level": "1", "id": "s3" } }, { "name": "p", "data": [ { "name": "text", "data": "从2016年第一篇刺激响应型AIE水凝胶研究报道至今只有6年，但已经在生物医学、信息防伪、3D水凝胶驱动器以及软体机器人开发等多个高科技领域展现出了广阔的应用前景。刺激响应型AIE水凝胶研究已经取得了若干重要进展，因此，对相关工作进行综述和点评是非常必要的。为了进一步促进刺激响应型AIE水凝胶的研究水平和实际应用转化，本综述从物理刺激(温度刺激响应、光刺激响应)、化学刺激(pH值刺激响应、溶剂刺激响应、离子刺激响应)以及生物刺激(酶刺激响应)三大方面对其进行归纳与总结，并阐述其在信息存储与防伪、生物医学、智能机器人等领域的潜在应用。但总的来说，刺激响应型AIE水凝胶的研究尚处于初级阶段，仍有很多问题需要进一步深入探索。在物理因素刺激方面，如可将力致变色或力致发光AIE材料引入水凝胶当中，对各种环境下的应力变化进行检测和响应，特别是微尺度下的可视化应力检查；在化学因素刺激方面，可以进一步丰富刺激手段，如开发对有毒药物、有毒气体、有毒离子、二氧化碳等的刺激响应性水凝胶，用于食品安全、公共安全、环境安全等领域；在生物因素刺激方面，可以进一步开发疾病标志物相关的刺激响应水凝胶，利用水凝胶材料易于微型化制备的优势，开发智能机器人用于生物医学研究等。此外，针对目前研究均为单一因素的刺激响应水凝胶，在今后的研究中可以开发双重或多重刺激响应的AIE水凝胶" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "50", "type": "bibr", "rid": "R50", "data": [ { "name": "text", "data": "50" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，在信息存储领域可以进一步增加材料对信息的存储量；在防伪领域提高信息的加密级别；在生物医学领域可以提高检测的准确性等。为了提高刺激响应性AIE水凝胶的应用能力，针对水凝胶材料的理化性质，可进一步提高材料的光学稳定性和机械强度；实现刺激条件与发光强度以及发光颜色的精准调控等。随着刺激响应性水凝胶材料研究的不断深入，相信其一定能够在更多的高科技领域发挥其独特的功能和作用，为人类社会的健康发展做出突出贡献。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "本文专家审稿意见及作者回复内容的下载地址：http://cjl.lightpublishing.cn/thesisDetails#10.37188/CJL.20220023." } ] } ] } ], "footnote": [], "reflist": { "title": [ { "name": "text", "data": "参考文献：" } ], "data": [ { "id": "R1", "label": "[1]", "citation": [ { "lang": "en", "text": [ { "name": "text", "data": "GHOBRIL C" }, { "name": "text", "data": ", " }, { "name": "text", "data": "GRINSTAFF M W" }, { "name": "text", "data": ". 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