具有pH响应性能的聚集诱导发光材料制备与表征

{ "defaultlang": "zh", "titlegroup": { "articletitle": [ { "lang": "zh", "data": [ { "name": "text", "data": "具有pH响应性能的聚集诱导发光材料制备与表征" } ] }, { "lang": "en", "data": [ { "name": "text", "data": "Synthesis and Characterization of pH-responsive Material with Aggregation-induced Emission Property" } ] } ] }, "contribgroup": { "author": [ { "name": [ { "lang": "zh", "surname": "王", "givenname": "嘉慧", "prefix": "" }, { "lang": "en", "surname": "WANG", "givenname": "Jia-hui", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" } ], "role": [ "first-author" ], "bio": [ { "lang": "zh", "text": [ "王嘉慧(1995－)，女，上海人，硕士研究生，2017年于华侨大学获得学士学位，主要从事手性液晶材料的制备及其圆偏振发光和相变行为的研究。E-mail: JiahuiWang0802@163.com" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348532&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348531&type=", "big": 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"surname": "LYU", "givenname": "Xu-chen", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" } ], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "任", "givenname": "相魁", "prefix": "" }, { "lang": "en", "surname": "REN", "givenname": "Xiang-kui", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" } ], "role": [ "corresp", "corresp" ], "corresp": [ { "rid": "cor1", "lang": "zh", "text": "任相魁(1980－)，男，河北邢台人，博士，副教授。2010年于南开大学物理学院获得理学博士学位；2007—2009年，美国Akron大学高分子科学与工程学院公派联合培养；2010—2012 年，北京大学化学与分子工程学院博士后；2012年12月开始在天津大学化工学院高分子系工作。研究方向为有机小分子及高分子材料的晶体结构、液晶结构及光电性质，研究范围涉及晶体/液晶发光材料、非线性光学、聚集诱导发光、传感器等。至今已在Angewandte Chemie International Edition，Chemical Society Reviews等期刊发表 SCI论文50余篇。", "data": [ { "name": "text", "data": "任相魁(1980－)，男，河北邢台人，博士，副教授。2010年于南开大学物理学院获得理学博士学位；2007—2009年，美国Akron大学高分子科学与工程学院公派联合培养；2010—2012 年，北京大学化学与分子工程学院博士后；2012年12月开始在天津大学化工学院高分子系工作。研究方向为有机小分子及高分子材料的晶体结构、液晶结构及光电性质，研究范围涉及晶体/液晶发光材料、非线性光学、聚集诱导发光、传感器等。至今已在Angewandte Chemie International Edition，Chemical Society Reviews等期刊发表 SCI论文50余篇。" } ] }, { "rid": "cor2", "lang": "en", "text": "E-mail: renxiangkui@tju.edu.cn", "data": [ { "name": "text", "data": "E-mail: renxiangkui@tju.edu.cn" } ] } ], "bio": [ { "lang": "zh", "text": [ "任相魁(1980－)，男，河北邢台人，博士，副教授，2010年于南开大学获得博士学位，主要从事小分子及高分子材料的晶体结构和光电性质的研究。E-mail: renxiangkui@tju.edu.cn" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348535&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348534&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348535&type=" } ], "data": [ [ { "name": "text", "data": "任相魁" }, { "name": "text", "data": "(1980－)，男，河北邢台人，博士，副教授，2010年于南开大学获得博士学位，主要从事小分子及高分子材料的晶体结构和光电性质的研究。E-mail: " }, { "name": "text", "data": "renxiangkui@tju.edu.cn" } ] ] } ], "email": "renxiangkui@tju.edu.cn", "deceased": false }, { "name": [ { "lang": "zh", "surname": "余", "givenname": "振强", "prefix": "" }, { "lang": "en", "surname": "YU", "givenname": "Zhen-qiang", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff2", "text": "2" } ], "role": [], "deceased": false } ], "aff": [ { "id": "aff1", "intro": [ { "lang": "zh", "label": "1", "text": "天津大学化工学院 化学工程联合国家重点实验室， 天津 　 300350；", "data": [ { "name": "text", "data": "天津大学化工学院 化学工程联合国家重点实验室， 天津 　 300350；" } ] }, { "lang": "en", "label": "1", "text": "State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China;", "data": [ { "name": "text", "data": "State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China;" } ] } ] }, { "id": "aff2", "intro": [ { "lang": "zh", "label": "2", "text": "深圳大学 化学与环境工程学院， 广东 深圳 　 518037", "data": [ { "name": "text", "data": "深圳大学 化学与环境工程学院， 广东 深圳 　 518037" } ] }, { "lang": "en", "label": "2", "text": "College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518037, China", "data": [ { "name": "text", "data": "College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518037, China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "聚集诱导发光(Aggregation-induced emission，AIE)由于在超分子化学、生物学以及材料科学方面起着非常重要的作用而受到人们的广泛关注。为拓展AIE分子在生物机体的内环境或自然环境中的应用，水溶性的AIE分子更是受到高度关注。本工作合成了以二氰基二苯乙烯基苯为发光基元、磺酸基为亲水基元的水溶性AIE分子DCS-SO" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "，并对其光物理性能进行了研究。光谱实验结果表明，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "能够以水作为良溶剂，并伴随着四氢呋喃的加入呈现聚集诱导发光的性质。同时，由于磺酸基具有可逆结合质子的能力，DCS-SO" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "可在酸性环境中结合H" }, { "name": "sup", "data": [ { "name": "text", "data": "＋" } ] }, { "name": "text", "data": "发生质子化，以DCS-SO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "H形式存在；在碱性环境中脱去质子，以" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的形式存在。因此，DCS-SO" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "是一种具有AIE性质和pH响应性能的新型亲水性材料。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "Aggregation-induced emission(AIE) luminogens have attracted considerable attention for its important role in supramolecular chemistry, biology and materials science, especially, those with water-solubility which were highlighted because of the application in the internal environment of biological organism or natural environment. In this work, a water-soluble AIE molecule(" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": ") with dicyanodistyrylbenzene(DCS) as the luminescent moiety and sulfonic group as the hydrophilic unit was synthesized, and its optical properties were systematically studied. Spectroscopic studies suggested that the addition of the poor solvent acetonitrile to the aqueous solution caused the formation of" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " nanoparticles and the AIE phenomena were demonstrated. Furthermore, as the sulfonic group has the ability to bind protons reversibly, the absorption peaks of DCS-SO" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " were blue-shift after the addition of acid. Moreover, the color change process was reversible upon pH change. By making use of the AIE property and chemical reactivity towards OH" }, { "name": "sup", "data": [ { "name": "text", "data": "-" } ] }, { "name": "text", "data": "/H" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": ", " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " is able to respond pH within the pH range from 1 to 13 by showing different emission colors and intensities: strong to weak blue emission within the pH range from 1 to 7 and weak blue emission to strong orange emission within the pH range from 8 to 13. According to AIE mechanism, the reason for pH-mediated optical properties of " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " was studied. Therefore, " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " is a new material with the AIE and pH-responsive properties." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "聚集诱导发光" } ], [ { "name": "text", "data": "pH响应" } ], [ { "name": "text", "data": "二氰基二苯乙烯基苯" } ], [ { "name": "text", "data": "酸碱调控" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "aggregation-induced emission" } ], [ { "name": "text", "data": "pH-responsive" } ], [ { "name": "text", "data": "dicyanodistyrylbenzene" } ], [ { "name": "text", "data": "acid-base regulation" } ] ] } ], "highlights": [], "body": [ { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "1　引言" } ], "level": "1", "id": "s1" } }, { "name": "p", "data": [ { "name": "text", "data": "发光材料由于具有独特优势而有着非常广泛的应用前景。然而，人们发现大多数有机发光分子在稀溶液中能发射出荧光，一旦发生聚集，分子间的π-π作用会使得激发态的能量以非辐射的方式耗散而使荧光猝灭，这一现象被称为聚集导致猝灭(Aggregation-caused quenching，ACQ)，这种现象无疑限制了发光材料的使用" }, { "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": "2", "type": "bibr", "rid": "R2", "data": [ { "name": "text", "data": "2" } ] } } ], "rid": [ "R1", "R2" ], "text": "1-2", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。2001年，唐本忠课题组首次观察到一种硅杂环戊二烯分子，在稀溶液中几乎不发光，但随着不良溶剂的加入，其发光强度随之增强，这一现象被命名为聚集诱导发光(Aggregation-induced emission，AIE)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "3", "type": "bibr", "rid": "R3", "data": [ { "name": "text", "data": "3" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "6", "type": "bibr", "rid": "R6", "data": [ { "name": "text", "data": "6" } ] } } ], "rid": [ "R3", "R4", "R5", "R6" ], "text": "3-6", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。AIE现象的本质主要是在稀溶液中，分子以单分子的形式存在，通过分子内运动使得能量以非辐射的方式耗散。当分子发生聚集时，非辐射能量耗散因空间位阻受到抑制，激发态能量主要以辐射的方式耗散，从而出现明显的荧光增强现象" }, { "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": "8", "type": "bibr", "rid": "R8", "data": [ { "name": "text", "data": "8" } ] } } ], "rid": [ "R7", "R8" ], "text": "7-8", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。AIE材料的出现解决了上述传统荧光材料的大部分问题。目前，大量具有AIE性质的有机荧光染料已经被广泛研究并成功应用于生物传感器、荧光探针以及生物成像等领域" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "R9", "data": [ { "name": "text", "data": "9" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "R10", "data": [ { "name": "text", "data": "10" } ] } } ], "rid": [ "R9", "R10" ], "text": "9-10", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。尽管许多研究人员已经证明AIE材料在生物及环境领域具有独特优势，但大多数AIE材料是疏水的，从而导致其在生物机体的内环境或自然环境中难以应用。为了克服这一不足，研究人员通常采用共组装或将离子盐类基团引入AIE体系等策略，实现开发水溶性荧光探针的目标" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "11", "type": "bibr", "rid": "R11", "data": [ { "name": "text", "data": "11" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } } ], "rid": [ "R11", "R12", "R13" ], "text": "11-13", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "二氰基二苯乙烯基苯(Dicyanodistyrylbenzene，DCS)作为具有AIE性质的有机荧光基团，可以通过引入不同的基团修饰获得具有不同性质的二氰基二苯乙烯基苯衍生物" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } } ], "rid": [ "R14", "R15", "R16", "R17" ], "text": "14-17", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。磺酸基作为离子盐类基团，兼具良好的亲水性和质子传递性能，将其与有机体系相结合，可获得理想的亲水性荧光染料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } } ], "rid": [ "R18", "R19", "R20", "R21" ], "text": "18-21", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。本工作将具有AIE性质的二氰基二苯乙烯基苯基团和具有亲水性且能灵敏感应OH" }, { "name": "sup", "data": [ { "name": "text", "data": "－" } ] }, { "name": "text", "data": "/H" }, { "name": "sup", "data": [ { "name": "text", "data": "＋" } ] }, { "name": "text", "data": "的磺酸基团相结合，合成了一种兼具AIE性质和pH响应性能的新型亲水性分子" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2　实验" } ], "level": "1", "id": "s2" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.1　试剂与仪器" } ], "level": "2", "id": "s2a" } }, { "name": "p", "data": [ { "name": "text", "data": "对羟基苯甲醛、1，4-苯二乙腈、1，4-丁磺酸内酯、乙醇钠、乙酸等化学药品购自萨恩化学技术(上海)有限公司，哌啶购自国药集团化学试剂有限公司，异丙醇(IPA)、乙醇(EtOH)、丙酮等有机溶剂购自深圳昌泰科技有限公司。药品及溶剂均为分析纯，无需纯化可直接使用。" } ] }, { "name": "p", "data": [ { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "H NMR和" }, { "name": "sup", "data": [ { "name": "text", "data": "13" } ] }, { "name": "text", "data": "C NMR分别采用VNMRS 400M核磁共振仪和Bruker AVANCE Ⅲ 600M核磁共振仪进行检测，溶剂为氘代二甲基亚砜(" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "-DMSO)，内标为四甲基硅烷(TMS)；高分辨质谱采用Q-Exactive Focus 型质谱仪测试；利用UV-8000型紫外-可见分光光度计测试样品的紫外-可见吸收光谱；利用F7000型荧光光谱仪测试样品的荧光光谱。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2．2　合成方法" } ], "level": "1", "id": "s3" } }, { "name": "p", "data": [ { "name": "text", "data": "合成路线如" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "所示。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的合成路线" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.1" } ], "title": [ { "name": "text", "data": "Synthetic routes of " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348538&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348546&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348542&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "向250 mL的双口烧瓶中装入对羟基苯甲醛(3.44 g，28.17 mmol)和对二苯乙腈(2.07 g，12.81 mmol)，投入磁力搅拌子。在氮气氛围下加入60 mL丙酮，搅拌并加热至80 ℃回流之后，通过注射器缓慢滴加哌啶，搅拌反应至过夜，用TLC跟踪反应进度。待反应原料消耗完毕，冷却反应体系至室温，析出大量黄色固体。抽滤并用甲醇、丙酮充分洗涤之后烘干称重，最终得DCS-OH 3.74 g，产率为77.4%。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "在50 mL的双口烧瓶中加入DCS-OH(2.00 g，5.49 mmol)、乙醇钠(1.85 g，27.01 mmol)，在氮气氛围下加入25 mL乙醇，搅拌30 min，溶液变为橙红色，称取丁基磺酸内酯(1.87 g，13.72 mmol)溶解在5 mL乙醇中，将混合溶液缓慢滴加到反应体系中，加热回流，通过TLC跟踪反应进程。待反应原料消耗完毕，冷却反应体系至室温，有橙红色固体析出，抽滤后将所得固体用甲醇重结晶，得到最终产物" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " 0.46 g，产率为47.6%。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　结果与讨论" } ], "level": "1", "id": "s4" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.1　目标产物确认" } ], "level": "2", "id": "s4a" } }, { "name": "p", "data": [ { "name": "text", "data": "以氘代二甲基亚砜为溶剂，对所得中间产物DCS-OH用核磁共振氢谱表征，其结果如" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "所示。" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "DCS-OH在" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "-DMSO中的400 MHz核磁共振氢谱" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.2" } ], "title": [ { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "H NMR spectrum(400 MHz, " }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "-DMSO) of DCS-OH" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348550&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348559&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348554&type=" } ] } }, { "name": "p", "data": [ { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "H NMR(400 MHz，" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "-DMSO)，" }, { "name": "italic", "data": [ { "name": "text", "data": "δ" } ] }, { "name": "text", "data": "：(TMS，10" }, { "name": "sup", "data": [ { "name": "text", "data": "－6" } ] }, { "name": "text", "data": "): 10.30(s，2H)，7.96(s，2H)，7.88(d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "＝8.0 Hz，4H)，7.80(s，4H)，6.91(d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "＝8.0 Hz，4H)。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "以" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "-DMSO为溶剂，对所得最终产物" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "进行核磁共振氢谱、碳谱以及质谱表征，其结果如" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "～" }, { "name": "xref", "data": { "text": "5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "5" } ] } }, { "name": "text", "data": "所示。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "在" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "-DMSO中的400 MHz核磁共振氢谱" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.3" } ], "title": [ { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "H NMR spectrum(400 MHz, " }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "-DMSO) of DCS-SO" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "H NMR(400 MHz，" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "-DMSO)，" }, { "name": "italic", "data": [ { "name": "text", "data": "δ" } ] }, { "name": "text", "data": "：(TMS，10" }, { "name": "sup", "data": [ { "name": "text", "data": "－6" } ] }, { "name": "text", "data": "): 7.95(d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "＝8.0 Hz，4H)，7.76(d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "＝6.0 Hz，6H)，7.08 (d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "＝8.0 Hz，4H)，4.05(s，8H)，1.79(d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "＝32 Hz，8H)。" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348564&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348574&type=", "big": 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"subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348580&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348588&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348584&type=" } ] } }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的高分辨质谱" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.5" } ], "title": [ { "name": "text", "data": "HRMS spectrum of " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348593&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348603&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348598&type=" } ] } }, { "name": "p", "data": [ { "name": "sup", "data": [ { "name": "text", "data": "13" } ] }, { "name": "text", "data": "C NMR(150 MHz，" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "-DMSO)，" }, { "name": "italic", "data": [ { "name": "text", "data": "δ" } ] }, { "name": "text", "data": "：(TMS，10" }, { "name": "sup", "data": [ { "name": "text", "data": "－6" } ] }, { "name": "text", "data": ")：161.26，143.87，132.32，131.79，126.50，126.16，117.08，115.42，106.51，68.20，51.48，28.35，22.32。 MALDI-TOF-MS：calcd for " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "：317.072 7。Found：317.071 9。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3．2　聚集诱导发光性质" } ], "level": "1", "id": "s5" } }, { "name": "p", "data": [ { "name": "text", "data": "因为" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的结构包含具有AIE性质的DCS基团和具有亲水性的磺酸基基团，所以我们选取水作为良溶剂；四氢呋喃(THF)能与水完全互溶，可作为不良溶剂，且H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O/THF的混合溶剂体系可以引起" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的聚集。因此，这里我们选取H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O/THF作为溶剂体系对该分子的AIE性质进行探究。" } ] }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图6(a)", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6(a)" } ] } }, { "name": "text", "data": "为" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的紫外-可见吸收光谱。在纯的水溶液中，DCS-SO" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的最大吸收峰位于327 nm。随着不良溶剂THF的加入，最大吸收波长逐渐红移到373 nm，并且吸收曲线在长波长段出现吸收拖尾，这是由于纳米颗粒的析出形成的光散射或Mie效应导致" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "22", "type": "bibr", "rid": "R22", "data": [ { "name": "text", "data": "22" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，证明此时分子确实发生了聚集" }, { "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": "。同时，我们研究了不同比例的混合溶剂中" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的荧光发射。如" }, { "name": "xref", "data": { "text": "图6(b)", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6(b)" } ] } }, { "name": "text", "data": "所示，在纯的水溶液中，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的荧光发射十分微弱。随着不良溶剂的比例增加，其荧光发射逐渐增强，在THF的体积分数为99%时，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的荧光强度增加了6倍，具有明显的AIE性质。这一现象可以用分子内振动受限(Restriction of intramolecular vibrations，RIV)机理" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "5", "type": "bibr", "rid": "R5", "data": [ { "name": "text", "data": "5" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "进行合理解释。在良溶剂中，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "以单分子形式存在，在单分子态下氰基的强烈振动会消耗激发态能量而导致荧光猝灭" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "24", "type": "bibr", "rid": "R24", "data": [ { "name": "text", "data": "24" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；随着不良溶剂的加入，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "分子开始发生聚集，分子内振动受到限制，此时能量主要以辐射的方式耗散，荧光强度开始增大，表现出典型的AIE性质" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "fig", "data": { "id": "F6", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图6" } ], "title": [ { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "在H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O/THF混合溶剂中的紫外-可见吸收光谱(a)和荧光光谱(b)(插图：不同含水量下的荧光强度倍率图)，浓度为1.0×10" }, { "name": "sup", "data": [ { "name": "text", "data": "－5" } ] }, { "name": "text", "data": " mol/L，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "＝330 nm。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.6" } ], "title": [ { "name": "text", "data": "UV-Vis absorption spectra(a) and photoluminescence (PL) spectra(b) of " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " in H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O/THF mixtures(Inset: plots of" }, { "name": "italic", "data": [ { "name": "text", "data": "I" } ] }, { "name": "text", "data": "/" }, { "name": "italic", "data": [ { "name": "text", "data": "I" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": " for " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " in H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O/THF mixtures). Concentration: 1.0×10" }, { "name": "sup", "data": [ { "name": "text", "data": "－5" } ] }, { "name": "text", "data": " mol/L, " }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "＝330 nm." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348608&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348618&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348613&type=" } ] } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.3　pH响应性质" } ], "level": "2", "id": "s5a" } }, { "name": "p", "data": [ { "name": "text", "data": "有趣的是，我们发现" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "对pH表现出较灵敏的响应。如" }, { "name": "xref", "data": { "text": "图7(a)", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7(a)" } ] } }, { "name": "text", "data": "所示，当浓度为1×10" }, { "name": "sup", "data": [ { "name": "text", "data": "－5" } ] }, { "name": "text", "data": " mol/L的" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "溶液的pH值在1～10范围内时，溶液为无色；当pH达到11时，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "溶液的颜色突变为明显的黄色。这一现象表明" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "可作为肉眼可见的pH探针进行应用。为进一步了解不同pH缓冲溶液中" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的吸收差异，我们利用紫外-可见吸收光谱进行探究。如" }, { "name": "xref", "data": { "text": "图7(b)", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7(b)" } ] } }, { "name": "text", "data": "所示，当pH" }, { "name": "text", "data": "<" }, { "name": "text", "data": "11时，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "在327 nm(" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "327" } ] }, { "name": "text", "data": ")处有明显的吸收，当pH≥11时，407 nm(" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "407" } ] }, { "name": "text", "data": ")处出现强吸收，最大吸收波长发生明显红移。这一现象可以用DCS-SO" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "与OH" }, { "name": "sup", "data": [ { "name": "text", "data": "－" } ] }, { "name": "text", "data": "/H" }, { "name": "sup", "data": [ { "name": "text", "data": "＋" } ] }, { "name": "text", "data": "的可逆化学反应解释。在酸性环境中，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "发生质子化，以DCS-SO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "H的形式存在；而随着碱性的逐渐增强，DCS-SO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "H开始逐步脱质子。当pH＝11时，部分DCS-SO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "H完全脱去质子(" }, { "name": "xref", "data": { "text": "图7(c)", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7(c)" } ] } }, { "name": "text", "data": ")，开始以" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的阴离子形式存在，从而表现出明显不同于酸性或弱碱性环境中的吸收特征" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。为了更进一步了解407 nm和327 nm波长处吸光度的变化，我们探究了吸光度比值" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "407" } ] }, { "name": "text", "data": "/" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "327" } ] }, { "name": "text", "data": "与pH的关系。如" }, { "name": "xref", "data": { "text": "图7(c)", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7(c)" } ] } }, { "name": "text", "data": "所示，当pH" }, { "name": "text", "data": "<" }, { "name": "text", "data": "11时，该比值基本保持不变。而当溶液的碱性继续增强至pH＝11时，比值迅速上升，这可能是由于部分DCS-SO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "H完全去质子化形成了富电子结构。此时" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "受到强给电子基团的影响，在分子激发跃迁过程中给电子基团到吸电子基团电荷转移更加显著，从给电子基团到缺电子基团发生分子内电荷转移，伴随着π-π" }, { "name": "sup", "data": [ { "name": "text", "data": "*" } ] }, { "name": "text", "data": "跃迁，从而出现更强和更宽的吸收峰。" } ] }, { "name": "fig", "data": { "id": "F7", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图7" } ], "title": [ { "name": "text", "data": "(a)" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "在不同pH缓冲溶液中的照片(pH＝1～13，从左到右，间隔为1)；(b)不同pH缓冲溶液中" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的紫外-可见吸收光谱(插图：" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "在pH＝9.24～11.39范围内的紫外-可见吸收光谱)；(c)" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "407" } ] }, { "name": "text", "data": "/" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "327" } ] }, { "name": "text", "data": "的比值与pH的关系图(" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "407" } ] }, { "name": "text", "data": "和" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "327" } ] }, { "name": "text", "data": "是在407 nm和327 nm波长处的吸光度)；(d)" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "在酸性、中性以及碱性环境下的紫外-可见吸收光谱；(e)" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的酸碱抗疲劳性测试。浓度为1.0×10" }, { "name": "sup", "data": [ { "name": "text", "data": "－5" } ] }, { "name": "text", "data": " mol/L。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.7" } ], "title": [ { "name": "text", "data": "(a)Photographs of " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " in buffer solutions taken under normal laboratory lighting are shown(pH＝1－13, from left to right with an interval of 1). (b)Variations of absorption spectra of " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " with pH in aqueous buffer solutions(Inset: UV-Vis absorption spectra of " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " within the pH range from 9.24 to 11.39). (c)Plot of " }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "407" } ] }, { "name": "text", "data": "/" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "327" } ] }, { "name": "text", "data": " " }, { "name": "italic", "data": [ { "name": "text", "data": "versus" } ] }, { "name": "text", "data": " pH value(where " }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "407" } ] }, { "name": "text", "data": " and " }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "327" } ] }, { "name": "text", "data": " are the absorbance at the wavelength of 407 nm and 327 nm, respectively) of " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " with pH in aqueous buffer solutions. (d)UV-Vis absorption spectra of " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " in acidic, neutral, and basic conditions. (e)Reversible switching of the absorption of" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " by repeated adjustment of its solution to acidic and basic environments. Concentration: 1.0×10" }, { "name": "sup", "data": [ { "name": "text", "data": "－5" } ] }, { "name": "text", "data": " mol/L." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348624&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348633&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348628&type=" } ] } }, { "name": "p", "data": [ { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "不但对于环境的酸碱性具有灵敏的响应，而且，这种响应是可逆的。通过调节" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "溶液为酸性(pH＝1)或碱性(pH＝13)(" }, { "name": "xref", "data": { "text": "图7(d)、(e)", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7(d)、(e)" } ] } }, { "name": "text", "data": ")，其相应的最大吸收波长可在327 nm和407 nm之间重复切换。这种响应非常快，并且具有多次可重复性，由此证明" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "有着良好的酸碱抗疲劳性。" } ] }, { "name": "p", "data": [ { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的荧光属性对pH的变化同样敏感。当" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "溶液的pH值从1增加到13时，其荧光从蓝色变为橙色。如" }, { "name": "xref", "data": { "text": "图8(a)", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8(a)" } ] } }, { "name": "text", "data": "所示，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "在强酸或强碱中均呈现较强发射，而在中性环境发射明显减弱。如" }, { "name": "xref", "data": { "text": "图8(b)", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8(b)" } ] } }, { "name": "text", "data": "所示，酸性环境中，溶液在440 nm处有较强发射，而当pH" }, { "name": "text", "data": ">" }, { "name": "text", "data": "11时，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "在440 nm处的发射几乎消失，在514 nm处出现较强发射。这一现象可以结合AIE的机制进行解释。如" }, { "name": "xref", "data": { "text": "图8(c)", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8(c)" } ] } }, { "name": "text", "data": "所示，在酸性环境中，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的磺酸基团充分质子化，粒子的疏水性增强，溶解度降低，开始形成DCS-SO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "H的紧密聚集体(" }, { "name": "xref", "data": { "text": "图8(b)", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8(b)" } ] } }, { "name": "text", "data": "区域Ⅰ)，分子内振动受到限制，荧光发射增强。随着pH增大，聚集体外部的DCS-SO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "H先脱去一端的质子，开始形成具有DCS-SO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "H核和HO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "S-" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "壳的聚集体。当溶液环境为中性时，聚集体内部的DCS-SO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "H开始脱质子，亲水性增强，但受更大体积的疏水基团影响，HO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "S-" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "在中性的pH缓冲溶液中很难完全分散。此时，水分子进入聚集体内部，使得HO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "S-" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "离子仅能形成松散的聚集体(" }, { "name": "xref", "data": { "text": "图8(b)", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8(b)" } ] } }, { "name": "text", "data": "区域Ⅱ)，分子内振动并未受到限制，发射开始减弱甚至消失。随着溶液环境变为碱性，HO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "S-" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的第二个质子也开始脱去，开始形成" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "，粒子的亲水性增强，亲水基团将疏水基团包裹在内部，水分子难以进入聚集体内部，大量的" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "离子开始聚集(" }, { "name": "xref", "data": { "text": "图8(b)", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8(b)" } ] } }, { "name": "text", "data": "区域Ⅲ)，发射逐渐增强" }, { "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": "。" } ] }, { "name": "fig", "data": { "id": "F8", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图8" } ], "title": [ { "name": "text", "data": "(a)" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "在不同pH缓冲溶液中的荧光照片(pH＝1～13，从左到右，间隔为1)；(b)" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "在不同pH缓冲溶液中的荧光光谱以及" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "在440 nm和514 nm处的归一化峰值与pH的关系图；(c)" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "的荧光随pH变化的机理示意图。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.8" } ], "title": [ { "name": "text", "data": "(a)Fluorescent photographs of " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " in buffer solutions excited by a hand-held UV lamp at an excitation wavelength of 365 nm (pH＝1－13, from left to right, interval: 1). (b)PL spectra of " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " in aqueous solutions at different pH values and the plots of normalized emission peak intensities at the specific wavelengths " }, { "name": "italic", "data": [ { "name": "text", "data": "versus" } ] }, { "name": "text", "data": " pH value. Concentration: 1.0×10" }, { "name": "sup", "data": [ { "name": "text", "data": "－5" } ] }, { "name": "text", "data": " mol/L; " }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "＝340 nm. (c)Proposed mechanism for fluorometric switching of DCS-SO" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": " in response to acid and base." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348638&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348647&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348643&type=" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4　结论" } ], "level": "1", "id": "s6" } }, { "name": "p", "data": [ { "name": "text", "data": "本文设计并合成了一种兼具AIE性质和pH响应性质的水溶性分子" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "，并通过核磁共振氢谱等方法确认了其分子结构。光谱实验结果表明，该材料具有典型的聚集诱导发光性质。同时，得益于磺酸基的可逆得失质子能力，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "在pH＝11且溶液浓度仅有1.0×10" }, { "name": "sup", "data": [ { "name": "text", "data": "－5" } ] }, { "name": "text", "data": " mol/L时发生了吸收和荧光变化，并伴有显著的颜色变化。此外，这种分子具有良好的酸碱抗疲劳性。这些实验结果说明" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "" } } ] }, { "name": "text", "data": "是一种新型高度灵敏性和精确性的pH响应材料，在环境检测以及生物应用领域具有潜在的应用价值。" } ] } ] } ], "footnote": [], "reflist": { "title": [ { "name": "text", "data": "参考文献：" } ], "data": [ { "id": "R1", "label": "[1]", "citation": [ { "lang": "zh", "text": [ { "name": "text", "data": "YUAN W Z" }, { "name": "text", "data": ", " }, { "name": "text", "data": "LU P" }, { "name": "text", "data": ", " }, { "name": "text", "data": "CHEN S M" }, { "name": "text", "data": ", " }, { "name": "text", "data": "et al" }, { "name": "text", "data": ". 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