An Aggregation-induced Emission Molecule Based on Gold Complex and Its Application for Hg²⁺ Detection

{ "defaultlang": "zh", "titlegroup": { "articletitle": [ { "lang": "zh", "data": [ { "name": "text", "data": "基于金配合物的聚集诱导发光分子合成及其对Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "的检测" } ] }, { "lang": "en", "data": [ { "name": "text", "data": "An Aggregation-induced Emission Molecule Based on Gold Complex and Its Application for Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " Detection" } ] } ] }, "contribgroup": { "author": [ { "name": [ { "lang": "zh", "surname": "汪", "givenname": "婷", "prefix": "" }, { "lang": "en", "surname": "WANG", "givenname": "Ting", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [], "role": [ "first-author" ], "bio": [ { "lang": "zh", "text": [ "汪婷(2000－)，女，安徽桐城人，在读本科生，主要从事聚集诱导发光材料的研究。E-mail: 2430471967@qq.com" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348544&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348541&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348544&type=" } ], "data": [ [ { "name": "text", "data": "汪婷" }, { "name": "text", "data": "(2000－)，女，安徽桐城人，在读本科生，主要从事聚集诱导发光材料的研究。E-mail: " }, { "name": "text", "data": "2430471967@qq.com" } ] ] } ], "email": "2430471967@qq.com", "deceased": false }, { "name": [ { "lang": "zh", "surname": "李", "givenname": "天浩", "prefix": "" }, { "lang": "en", "surname": "LI", "givenname": "Tian-hao", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "张", "givenname": "雨", "prefix": "" }, { "lang": "en", "surname": "ZHANG", "givenname": "Yu", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "魏", "givenname": "禧龙", "prefix": "" }, { "lang": "en", "surname": "WEI", "givenname": "Xi-long", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "白", "givenname": "冰", "prefix": "" }, { "lang": "en", "surname": "BAI", "givenname": "Bing", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "刘", "givenname": "园园", "prefix": "" }, { "lang": "en", "surname": "LIU", "givenname": "Yuan-yuan", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "李", "givenname": "恺", "prefix": "" }, { "lang": "en", "surname": "LI", "givenname": "Kai", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [], "role": [ "corresp", "corresp" ], "corresp": [ { "rid": "cor1", "lang": "zh", "text": "李恺(1985－)，男，河南郑州人，博士，副教授。2014年于清华大学化学系获得理学博士学位；2012年和2017年，中国香港科技大学化学系Research Associate；2014年入职郑州大学化学学院。研究方向为刺激响应型聚集诱导发光材料和团簇基聚集诱导发光材料。主持国家基金两项，河南省优秀青年基金一项，发表SCI论文60余篇。", "data": [ { "name": "text", "data": "李恺(1985－)，男，河南郑州人，博士，副教授。2014年于清华大学化学系获得理学博士学位；2012年和2017年，中国香港科技大学化学系Research Associate；2014年入职郑州大学化学学院。研究方向为刺激响应型聚集诱导发光材料和团簇基聚集诱导发光材料。主持国家基金两项，河南省优秀青年基金一项，发表SCI论文60余篇。" } ] }, { "rid": "cor3", "lang": "en", "text": "E-mail: likai@zzu.edu.cn;", "data": [ { "name": "text", "data": "E-mail: likai@zzu.edu.cn;" } ] } ], "bio": [ { "lang": "zh", "text": [ "李恺(1985－)，男，河南郑州人，博士，副教授，2014年于清华大学获得博士学位，主要从事聚集诱导发光材料的研究。E-mail: likai@zzu.edu.cn" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348558&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348553&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348558&type=" } ], "data": [ [ { "name": "text", "data": "李恺" }, { "name": "text", "data": "(1985－)，男，河南郑州人，博士，副教授，2014年于清华大学获得博士学位，主要从事聚集诱导发光材料的研究。E-mail: " }, { "name": "text", "data": "likai@zzu.edu.cn" } ] ] } ], "email": "likai@zzu.edu.cn", "deceased": false }, { "name": [ { "lang": "zh", "surname": "臧", "givenname": "双全", "prefix": "" }, { "lang": "en", "surname": "ZANG", "givenname": "Shuang-quan", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [], "role": [ "corresp", "corresp" ], "corresp": [ { "rid": "cor2", "lang": "zh", "text": "臧双全(1976－)，男，国家杰出青年基金获得者，英国皇家化学学会会士，享受国务院政府特殊津贴，第十批河南省优秀专家，博士研究生导师，宝钢优秀教师，河南省特聘教授，获河南省自然科学一等奖1项。现任郑州大学化学学院主持工作副院长，绿色催化中心主持工作副主任。担任中国化学会分子聚集发光专业委员会副主任委员，中国化学会分子筛专业委员会委员，中国化学会晶体化学专业委员会委员，河南省化学学会第十一届理事会副理事长，Wiley期刊Aggregate Associate Editor，ACS期刊Crystal Growth & Design Topic Editor(2020—2021)，《无机化学学报》编委、《中国化学》和《结构化学》青年编委。主要研究方向为金属簇化学和金属有机框架材料。主持包括重大研究计划重点支持项目、国家杰出青年基金项目、面上项目等多项国家级和省部级重要科研项目。在Chem. Soc. Rev., Nat. Chem., Nat. Commun. Sci. Adv., J. Am. Chem. Soc., Angew. Chem. Int. Ed., Adv. Mater.等权威化学类期刊发表SCI论文180余篇。代表性论文被国际著名刊物Chem. Rev., Chem. Soc. Rev., J. Am. Chem. Soc., Angew. Chem. Int. Ed.等引用8 700余次， H-index＝52。 2011及2012年在“Nova Science Publishers”出版的两本英文专业论著以第一作者和通讯作者撰写其中两个章节。授权国家发明专利10项。受邀为Sci. Adv., Nat. Commun., J. Am. Chem. Soc., Angew. Chem. Int. Ed., Adv. Mater.等国际权威期刊审稿人。", "data": [ { "name": "text", "data": "臧双全(1976－)，男，国家杰出青年基金获得者，英国皇家化学学会会士，享受国务院政府特殊津贴，第十批河南省优秀专家，博士研究生导师，宝钢优秀教师，河南省特聘教授，获河南省自然科学一等奖1项。现任郑州大学化学学院主持工作副院长，绿色催化中心主持工作副主任。担任中国化学会分子聚集发光专业委员会副主任委员，中国化学会分子筛专业委员会委员，中国化学会晶体化学专业委员会委员，河南省化学学会第十一届理事会副理事长，Wiley期刊Aggregate Associate Editor，ACS期刊Crystal Growth & Design Topic Editor(2020—2021)，《无机化学学报》编委、《中国化学》和《结构化学》青年编委。主要研究方向为金属簇化学和金属有机框架材料。主持包括重大研究计划重点支持项目、国家杰出青年基金项目、面上项目等多项国家级和省部级重要科研项目。在Chem. Soc. Rev., Nat. Chem., Nat. Commun. Sci. Adv., J. Am. Chem. Soc., Angew. Chem. Int. Ed., Adv. Mater.等权威化学类期刊发表SCI论文180余篇。代表性论文被国际著名刊物Chem. Rev., Chem. Soc. Rev., J. Am. Chem. Soc., Angew. Chem. Int. Ed.等引用8 700余次， H-index＝52。 2011及2012年在“Nova Science Publishers”出版的两本英文专业论著以第一作者和通讯作者撰写其中两个章节。授权国家发明专利10项。受邀为Sci. Adv., Nat. Commun., J. Am. Chem. Soc., Angew. Chem. Int. Ed., Adv. Mater.等国际权威期刊审稿人。" } ] }, { "rid": "cor4", "lang": "en", "text": "zangsqzg@zzu.edu.cn", "data": [ { "name": "text", "data": "zangsqzg@zzu.edu.cn" } ] } ], "bio": [ { "lang": "zh", "text": [ "臧双全(1976－)，男，河南驻马店人，博士，教授，2006年于南京大学获得博士学位，主要从事货币金属团簇材料的研究。E-mail: zangsqzg@zzu.edu.cn" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348573&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348568&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348573&type=" } ], "data": [ [ { "name": "text", "data": "臧双全" }, { "name": "text", "data": "(1976－)，男，河南驻马店人，博士，教授，2006年于南京大学获得博士学位，主要从事货币金属团簇材料的研究。E-mail: " }, { "name": "text", "data": "zangsqzg@zzu.edu.cn" } ] ] } ], "email": "zangsqzg@zzu.edu.cn", "deceased": false } ], "aff": [ { "id": "aff1", "intro": [ { "lang": "zh", "text": "郑州大学化学学院 绿色催化中心， 河南 郑州 　 450001", "data": [ { "name": "text", "data": "郑州大学化学学院 绿色催化中心， 河南 郑州 　 450001" } ] }, { "lang": "en", "text": "Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou 450001, China", "data": [ { "name": "text", "data": "Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou 450001, China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "设计合成了一种新型聚集诱导发光分子三苯乙烯炔金-三苯基膦(1)。1溶解在DMSO中几乎无荧光，在固体状态下具有明亮的蓝色荧光，表现出典型的聚集诱导发光性能。研究表明，其聚集诱导发光特性来自于限制分子内旋转机理。1在水溶液中表现出对Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "的荧光猝灭响应，并表现出良好的选择性和抗干扰能力。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "A new aggregation-induced emission(AIE) molecule of triphenylvinylacetylene gold triphenylphosphine complex(1) was designed and synthesized in this work. 1 showed no emission in DMSO solution but intense emission in solid state, suggesting a typical AIE property. The AIE property of 1 was proven to be originated from a restriction of intramolecular rotation(RIR) mechanism. A fluorescence \"turn-off\" response of 1 for Hg " }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " ion was observed in aqueous solution, which exhibited good selectivity and anti-interference property." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "聚集诱导发光" } ], [ { "name": "text", "data": "金配合物" } ], [ { "name": "text", "data": "汞离子检测" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "aggregation-induced emission" } ], [ { "name": "text", "data": "gold complex" } ], [ { "name": "text", "data": "Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " detection" } ] ] } ], "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": "有机发光材料在荧光传感器、发光器件等领域应用广泛" }, { "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": "8", "type": "bibr", "rid": "R8", "data": [ { "name": "text", "data": "8" } ] } } ], "rid": [ "R1", "R2", "R3", "R4", "R5", "R6", "R7", "R8" ], "text": "1-8", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。然而，大多数有机发光材料在稀溶液中荧光较强，在浓溶液或聚集态时发光弱或者不发光，这种“聚集引起荧光猝灭”(ACQ)现象极大地限制了有机发光材料的应用" }, { "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": "11", "type": "bibr", "rid": "R11", "data": [ { "name": "text", "data": "11" } ] } } ], "rid": [ "R9", "R10", "R11" ], "text": "9-11", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。2001年，唐本忠教授课题组报道了一种与ACQ效应相反的光学现象：聚集诱导发光(AIE)现象，即在溶液态几乎不发光，聚集态或固态下均有强荧光" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "12", "type": "bibr", "rid": "R12", "data": [ { "name": "text", "data": "12" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。这种独特的发光性质使AIE分子在有机发光二极管、生物探针传感器、刺激响应材料等生物、化学领域得到了广泛应用" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } } ], "rid": [ "R13", "R14", "R15", "R16", "R17" ], "text": "13-17", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "经过近20年的发展，包括有机小分子、高分子聚合物、金属团簇、配合物、碳量子点等在内的数以千计的AIE分子被合成报道" }, { "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": "23", "type": "bibr", "rid": "R23", "data": [ { "name": "text", "data": "23" } ] } } ], "rid": [ "R18", "R19", "R20", "R21", "R22", "R23" ], "text": "18-23", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，表现出优异的性能。然而，目前报道的绝大多数AIE体系都为有机分子，对于有机无机杂化AIE体系的研究仍比较有限。开发性能优异、成本低廉的新型有机无机杂化AIE体系具有十分重要的意义。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "在本研究中，我们开发了一种新型有机无机杂化AIE体系——三苯乙烯炔金-三苯基膦(1)。该体系合成简单，反应条件温和，产率达到90%，且原料成本十分低廉。1在溶液中不发光，聚集态和固态时表现出强烈的荧光，具有典型的AIE特性。研究表明，1具有典型的螺旋桨状结构，其中含有多个可旋转的苯环，其AIE特性来自于限制分子内旋转机理。有趣的是，1的水溶液对Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "表现出猝灭荧光现象，能选择性地检测Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "，检测限达到0.59 μmol/L。" } ] } ] }, { "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　试剂和仪器" } ], "level": "2", "id": "s2a" } }, { "name": "p", "data": [ { "name": "text", "data": "二甲亚砜(DMSO)、四氢呋喃(THF)、甲醇(MeOH)、甘油均为分析纯，国药集团化学试剂有限公司，购买后直接使用。去离子水(蒸馏水)和DMSO在整个实验中使用。实验中使用的金属离子溶液均由其硝酸盐制备而成。 " }, { "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由Bruker AV-400和Bruker AV-600核磁共振波谱仪记录；元素分析由Perkin-Elmer 240元素分析仪记录；紫外光谱由Hitachi UH4150紫外-可见分光光度仪记录；荧光光谱由HORIBA FluoroLog-3荧光光谱仪记录；动态光散射数据由Horiba nano Partica SZ-100V2型Zeta电位仪测试得到；X射线单晶衍射数据由Rigaku XtaLAB Pro单晶衍射仪收集；质谱由X500R QTOF质谱测试仪确定。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.2　化合物1的合成" } ], "level": "2", "id": "s2b" } }, { "name": "p", "data": [ { "name": "text", "data": "1的合成路线如" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "所示，三苯基膦氯化金(PPh" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "AuCl)按文献[" }, { "name": "xref", "data": { "text": "24", "type": "bibr", "rid": "R24", "data": [ { "name": "text", "data": "24" } ] } }, { "name": "text", "data": "]方法合成。按文献[" }, { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } }, { "name": "text", "data": "]方法合成1，1，2-三苯基-1-丁烯-3-炔(1a)，即在50 mL 三乙胺溶液中加入溴-三苯基乙烯(3.35 g，10.0 mmol)、三甲基硅基乙炔(2.14 mL，15.0 mmol)、PdCl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(PPh" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": ")" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(140 mg，0.199 mmol)和CuI(19 mg，0.10 mmol)。反应混合物在70 ℃下加热搅拌16 h，饱和有机层用蒸馏水(3×100 mL)和盐水(3×100 mL)洗涤，无水硫酸镁干燥，减压蒸发。粗产品以" }, { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "正己烷" } ] }, { "name": "text", "data": "∶" }, { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "乙醚" } ] }, { "name": "text", "data": "＝100∶1的混合溶剂为展开剂通过柱层析法分离提纯，得到黄色油状液体。将黄色油状液体溶解于50 mL THF中，冷却至0 ℃，加入四丁基氟化铵(1.0 mol/L 的THF溶液，11 mL，11 mmol)，反应混合液加热至室温，搅拌1 h，缓慢加入饱和冷NaHCO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "溶液(50 mL)，然后用Et" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O(50 mL)稀释。有机层用蒸馏水(3×100 mL)和盐水(3×100 mL)洗涤，无水硫酸镁干燥，减压蒸发。粗产品以" }, { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "正己烷" } ] }, { "name": "text", "data": "∶" }, { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "乙醚" } ] }, { "name": "text", "data": "＝100∶1的混合溶剂为展开剂，通过柱层析法分离提纯得到1a。 " }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "H NMR(400 MHz，CDCl" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": ") " }, { "name": "italic", "data": [ { "name": "text", "data": "δ" } ] }, { "name": "text", "data": "(10" }, { "name": "sup", "data": [ { "name": "text", "data": "－6" } ] }, { "name": "text", "data": "): 7.49(d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "＝4.0 Hz，2H)，7.34(q，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "＝8.0 Hz，3H)，7.28(d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "＝4.0 Hz，2H)，7.12(m，6H)，6.96(d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "＝4.0 Hz，2H)，3.04(s，1H)。" }, { "name": "sup", "data": [ { "name": "text", "data": "13" } ] }, { "name": "text", "data": "C NMR(400 MHz，CDCl" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": ") " }, { "name": "italic", "data": [ { "name": "text", "data": "δ" } ] }, { "name": "text", "data": "(10" }, { "name": "sup", "data": [ { "name": "text", "data": "－6" } ] }, { "name": "text", "data": "): 150.49，142.37，141.17，139.37，130.99，130.27，129.94，128.07，127.94，127.83，127.82，127.40，127.15，120.43，85.65，81.17。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "化合物1的合成" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.1" } ], "title": [ { "name": "text", "data": "Synthesis of 1" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348578&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348590&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348583&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "将1a(48 mg，0.01 mmol)和PPh" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "AuCl(28 mg，0.01 mmol)分别溶于THF(5 mL)和MeOH(3 mL)的混合溶液中，两者混合均匀，然后向其中加入NaOH(25 mg，0.625 mmol)的甲醇(2 mL)溶液。常温避光搅拌12 h，减压蒸馏除去溶剂，粗产品以" }, { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "石油醚" } ] }, { "name": "text", "data": "∶" }, { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "乙酸乙酯" } ] }, { "name": "text", "data": "＝ 5∶1的混合溶剂为展开剂通过柱层析法分离提纯，得到淡黄色固体，产率90%。 " }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "H NMR(600 MHz，DMSO-" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": ")" }, { "name": "italic", "data": [ { "name": "text", "data": "δ" } ] }, { "name": "text", "data": "(10" }, { "name": "sup", "data": [ { "name": "text", "data": "－6" } ] }, { "name": "text", "data": "): 6.87(d，2H，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "＝6.0 Hz)，7.10(m，6H)，7.19(d，2H，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "＝6.0 Hz)，7.26(t，1H，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "＝6.0 Hz)，7.33(t，2H，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "＝6.0 Hz)，7.49(m，8H)，7.60(m，9H)。" }, { "name": "sup", "data": [ { "name": "text", "data": "13" } ] }, { "name": "text", "data": "C NMR(DMSO-" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": ") " }, { "name": "italic", "data": [ { "name": "text", "data": "δ" } ] }, { "name": "text", "data": "(600 MHz，10" }, { "name": "sup", "data": [ { "name": "text", "data": "－6" } ] }, { "name": "text", "data": "): 145.47，143.12，142.41，141.89，134.36，132.40，131.12，130.49，130.11，130.04，129.92，129.55，128.22，128．13，127.78，127.15，126.90，123.46，93.11，55.38。高分辨质谱： " }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "/" }, { "name": "italic", "data": [ { "name": "text", "data": "z" } ] }, { "name": "text", "data": " [C" }, { "name": "sub", "data": [ { "name": "text", "data": "40" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "30" } ] }, { "name": "text", "data": "AuP ＋ Cs]" }, { "name": "sup", "data": [ { "name": "text", "data": "＋" } ] }, { "name": "text", "data": " 理论值： 871.080 5; 测试值： 871.051 4。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　结果与讨论" } ], "level": "1", "id": "s3" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.1　化合物1的聚集诱导发光性质" } ], "level": "2", "id": "s3a" } }, { "name": "p", "data": [ { "name": "text", "data": "我们首先研究了化合物1的发光性能。将1溶于一系列不同体积配比的DMSO/H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O中，配制成浓度为10 μmol/L的若干组溶液(" }, { "name": "xref", "data": { "text": "图2(a)", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2(a)" } ] } }, { "name": "text", "data": ")。如" }, { "name": "xref", "data": { "text": "图2(b)", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2(b)" } ] } }, { "name": "text", "data": "所示，1在纯DMSO溶液中几乎不发光；但随着水含量增加至40%(体积分数，下同)时，溶液的荧光明显增强；当含水量为70%时，482 nm处的蓝色荧光强度急剧增强。与纯DMSO溶液中的荧光强度相比，1含水量为70%的体系中，1在482 nm处的荧光强度增大了118倍(" }, { "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)化合物1在不同H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O/DMSO含量溶液中的荧光照片；(b)化合物1在不同H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O/DMSO含量溶液中的荧光光谱；(c) 不同水含量下，化合物1在482 nm处的荧光强度。条件：[1]＝10 μmol/L，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "＝344 nm，照片在365 nm的紫外灯下拍摄。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.2" } ], "title": [ { "name": "text", "data": "(a)Fluorescence photo of 1 in water/DMSO mixtures with different " }, { "name": "italic", "data": [ { "name": "text", "data": "f" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "w" } ] }, { "name": "text", "data": ". (b)Fluorescence spectra of 1 in water/DMSO mixtures with different " }, { "name": "italic", "data": [ { "name": "text", "data": "f" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "w" } ] }, { "name": "text", "data": ". (c)Fluorescence intensity of 1 at 482 nm as a function of " }, { "name": "italic", "data": [ { "name": "text", "data": "f" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "w" } ] }, { "name": "text", "data": ". Conditions: [1]＝10 μmol/L," }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "＝344 nm, the photographs were taken under irradiation by 365 nm UV light." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348594&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348604&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348599&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "进一步，我们测试了1的紫外吸收光谱，如" }, { "name": "xref", "data": { "text": "图3(a)", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3(a)" } ] } }, { "name": "text", "data": "所示。纯水中的紫外吸收光谱与纯DMSO中的紫外吸收光谱相比，在可见光区域中可清楚地观察到拖尾现象，这种现象被认为是由聚集悬浮体颗粒的光散射导致的" }, { "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": "27", "type": "bibr", "rid": "R27", "data": [ { "name": "text", "data": "27" } ] } } ], "rid": [ "R26", "R27" ], "text": "26-27", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。其次，动态光散射实验表明， 1 在99%的DMSO/H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O混合溶剂中形成了直径165 nm左右的颗粒。这些结果均表明 1在纯DMSO中是溶解状态，而在高水含量溶液中为聚集状态。此外，在固态下，1表现出强烈的蓝色荧光，最大发射波长为455 nm(" }, { "name": "xref", "data": { "text": "图3(b)", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3(b)" } ] } }, { "name": "text", "data": ")，四苯乙烯的最大激发波长为458 nm，两者相差不大；1量子产率为13%，低于四苯乙烯的固体量子产率(49%)；寿命为0.37 ns，与四苯乙烯的寿命同为纳秒级别。以上实验结果表明，1是一个典型的有机无机杂化AIE分子。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "(a)化合物1在不同H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O/DMSO体积含量溶液中的紫外吸收光谱，插图：化合物1在99% H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O/DMSO(" }, { "name": "italic", "data": [ { "name": "text", "data": "v" } ] }, { "name": "text", "data": "/" }, { "name": "italic", "data": [ { "name": "text", "data": "v" } ] }, { "name": "text", "data": ")水溶液中的动态光散射实验测试；(b)化合物1在固态下的最佳激发发射光谱，插图：化合物1在日光(左图)和365 nm紫外光(右图)下的照片。条件：[1]＝10 μmol/L。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.3" } ], "title": [ { "name": "text", "data": "(a)Absorption spectra of 1 in water/DMSO mixtures with different " }, { "name": "italic", "data": [ { "name": "text", "data": "f" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "w," } ] }, { "name": "text", "data": " inset: DLS results of 1 in aqueous solution of 99% water/DMSO(" }, { "name": "italic", "data": [ { "name": "text", "data": "v" } ] }, { "name": "text", "data": "/" }, { "name": "italic", "data": [ { "name": "text", "data": "v" } ] }, { "name": "text", "data": "). (b)Fluorescence excitation and emission spectra of 1 in solid state, inset: photographs of 1 in solid state excited by sunlight(left) and 365 nm UV light(right). Conditions: [1]＝10 μmol/L." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348609&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348619&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348614&type=" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2　化合物1聚集诱导发光性质的来源" } ], "level": "2", "id": "s3b" } }, { "name": "p", "data": [ { "name": "text", "data": "为了探究化合物1聚集诱导发光性质的来源，我们对其晶体结构进行了研究。首先，在甲醇和二氯甲烷的混合溶剂中，通过缓慢的溶剂蒸发手段得到了1的晶体。利用单晶 X射线衍射仪确定了1的晶体结构。如" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "所示，1 的分子结构中含有多个以碳-碳单键相连的“可自由旋转”的苯环。在稀溶液中，这些苯环发生动态的分子内旋转，导致激发态电子以非辐射跃迁的形式回到基态，引起荧光猝灭。而浓溶液中(聚集态)或固态条件下，苯环的分子内旋转受到限制(Restriction of intramolecular rotation，RIR)，非辐射跃迁过程受阻，使辐射跃迁成为电子从激发态跃迁到基态的主要途径，从而产生强烈的荧光。同时，晶体结构表明，相邻分子中苯环的距离为0.440 3 nm，分子中不存在p-p堆积作用。因此，1的AIE性能很可能源自RIR过程。为证明RIR过程的合理性，我们测试了高粘度溶剂(DMSO/甘油)中化合物1的荧光。如" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "所示，随着甘油含量的增加，1的荧光逐渐增强，甘油体积分数达到99%时，荧光强度达到最大。这种荧光增强现象是由于溶剂粘度的逐步升高，1的分子内苯环旋转受限程度越来越严重，辐射跃迁通道逐渐打开，荧光增强。" } ] }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "化合物 1的晶体结构" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.4" } ], "title": [ { "name": "text", "data": "Crystal structure of 1" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348623&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348634&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348629&type=" } ] } }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "(a)化合物1在不同甘油/DMSO体积含量溶液中的荧光光谱；(b)不同甘油含量下，化合物1在482 nm处的荧光强度。条件：[1]＝10 μmol/L，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "＝344 nm。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.5" } ], "title": [ { "name": "text", "data": "(a)Fluorescence spectra of 1 in water/DMSO mixtures with different " }, { "name": "italic", "data": [ { "name": "text", "data": "f" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "w" } ] }, { "name": "text", "data": ". (b)Fluorescence intensity of 1 at 482 nm as a function of " }, { "name": "italic", "data": [ { "name": "text", "data": "f" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "w" } ] }, { "name": "text", "data": ". Conditions: [1]＝10 μmol/L," }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "＝344 nm." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348640&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348650&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348645&type=" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.3　化合物1对Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "的选择性荧光响应" } ], "level": "2", "id": "s3c" } }, { "name": "p", "data": [ { "name": "text", "data": "化合物1对Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "离子表现出了独特的响应性能。随着Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "的加入，化合物1水溶液的荧光逐渐猝灭(" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": ")。如" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "所示，分别在10 μmol/L的1的99%水溶液中加入7.5倍量的Na" }, { "name": "sup", "data": [ { "name": "text", "data": "＋" } ] }, { "name": "text", "data": "、K" }, { "name": "sup", "data": [ { "name": "text", "data": "＋" } ] }, { "name": "text", "data": "、Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "、Mg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "、Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "、Al" }, { "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": "、Pb" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "、Cr" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "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": "、Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "、Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "离子，1的荧光信号只有在Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "加入后发生了明显的变化。相同条件下加入其他金属离子时，1的荧光信号变化不明显，说明1对Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "的荧光响应具有很好的选择性。抗干扰能力测试表明，在不同金属离子存在的溶液中加入Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "后，荧光信号的变化强度与空白组中加入Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "后荧光信号的变化强度相近。这说明1对Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "的荧光响应具有很好的抗干扰能力，可以作为Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "的猝灭型荧光探针使用。根据文献报道，Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "可以与炔基结合，促使其发生水解反应，导致炔键被破坏" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "28", "type": "bibr", "rid": "R28", "data": [ { "name": "text", "data": "28" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。因此，化合物1对Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "的选择性响应很可能是由于1中的炔基与Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "发生反应导致的。为了证明我们的猜测，我们在1中加入Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "离子后，继续加入过量EDTA，发现其荧光并未恢复，证明1与Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "发生了不可逆反应(" }, { "name": "xref", "data": { "text": "图8(a)", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8(a)" } ] } }, { "name": "text", "data": ")。此外，为了进一步证明该机理，我们在DMSO-" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "中对1加入Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "前后的核磁进行了测定。如" }, { "name": "xref", "data": { "text": "图8(b)", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8(b)" } ] } }, { "name": "text", "data": "所示，在加入Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "前后，1的质子信号峰基本都没有发生改变，这说明Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "并未与金配合物中除炔键以外的部分发生化学反应，化学反应只可能发生在炔键部分，进一步印证了我们的推测。此外，由于反应后荧光没有完全猝灭，也从侧面证明生成的新化合物依然包含具有AIE性能的三苯乙烯基团。" } ] }, { "name": "fig", "data": { "id": "F6", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图6" } ], "title": [ { "name": "text", "data": "(a)化合物1水溶液中加入不同量Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "后荧光光谱的变化；(b)不同Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "含量下，化合物1在482 nm处的荧光强度。条件：[1]＝10 μmol/L，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "＝344 nm。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.6" } ], "title": [ { "name": "text", "data": "(a)Fluorescence spectra of 1 upon the addition of Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": ". (b)Fluorescence intensity of 1 at 482 nm as a function of Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": " concentration. Conditions: [1]＝10 μmol/L," }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "＝344 nm." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348654&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348660&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348657&type=" } ] } }, { "name": "fig", "data": { "id": "F7", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图7" } ], "title": [ { "name": "text", "data": "化合物1水溶液中加入不同金属离子以及不同金属离子和Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "离子后荧光信号的变化。从左至右依次为空白、Li" }, { "name": "sup", "data": [ { "name": "text", "data": "＋" } ] }, { "name": "text", "data": "、Na" }, { "name": "sup", "data": [ { "name": "text", "data": "＋" } ] }, { "name": "text", "data": "、K" }, { "name": "sup", "data": [ { "name": "text", "data": "＋" } ] }, { "name": "text", "data": "、Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "、Mg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "、Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "、Al" }, { "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": "、Pb" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "、Cr" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "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": "、Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "。条件：[1]＝10 μmol/L，[" }, { "name": "italic", "data": [ { "name": "text", "data": "M" } ] }, { "name": "text", "data": "]＝[Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "]＝75 μmol/L。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.7" } ], "title": [ { "name": "text", "data": "Fluorescence signal of 1 upon the addition of different metal ions in the absence and presence of Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": ". Ions from left to right are blank, Li" }, { "name": "sup", "data": [ { "name": "text", "data": "＋" } ] }, { "name": "text", "data": "， Na" }, { "name": "sup", "data": [ { "name": "text", "data": "＋" } ] }, { "name": "text", "data": "， K" }, { "name": "sup", "data": [ { "name": "text", "data": "＋" } ] }, { "name": "text", "data": "， Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "， Mg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "， Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "， Al" }, { "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": "， Pb" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "， Cr" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "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": " and Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": ". Conditions: [1]＝10 μmol/L, [" }, { "name": "italic", "data": [ { "name": "text", "data": "M" } ] }, { "name": "text", "data": "]＝[Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "]＝75 μmol/L." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348663&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348669&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348667&type=" } ] } }, { "name": "fig", "data": { "id": "F8", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图8" } ], "title": [ { "name": "text", "data": "(a) 化合物1在水溶液中的荧光光谱、加入Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "后的荧光光谱以及加入Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "后再加过量EDTA的荧光光谱，条件：[1]＝10 μmol/L，[Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "]＝75 μmol/L，[EDTA]" }, { "name": "text", "data": "＝150 μmol/L；(b)化合物1加入Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "前后的氢谱。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.8" } ], "title": [ { "name": "text", "data": "(a)Fluorescence emission spectra of 1 in aqueous solution before and after the addition of Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": " and EDTA. Conditions: [1]＝10 μmol/L, [Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "]＝75 μmol/L, [EDTA]" }, { "name": "text", "data": "＝150 μmol/L. (b)" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "H-NMR spectra of 1 in DMSO-" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": " before and after the addition of Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348673&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348679&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348677&type=" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.4　化合物1对Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "的定量检测性能" } ], "level": "2", "id": "s3d" } }, { "name": "p", "data": [ { "name": "text", "data": "为了表征化合物1对Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "的定量检测性能，我们利用1在水溶液中进行了Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "荧光滴定实验，实验结果如" }, { "name": "xref", "data": { "text": "图9", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9" } ] } }, { "name": "text", "data": "所示。在0.0～6.0 μmol/L范围内，化合物1在482 nm处的荧光强度与Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "的加入量呈现良好的线性关系，相关系数" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "＝0.99。根据 IUPAC的定义(" }, { "name": "italic", "data": [ { "name": "text", "data": "C" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "DL" } ] }, { "name": "text", "data": "＝3" }, { "name": "italic", "data": [ { "name": "text", "data": "S" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "b" } ] }, { "name": "text", "data": "/" }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "，其中" }, { "name": "italic", "data": [ { "name": "text", "data": "C" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "DL" } ] }, { "name": "text", "data": "是检测限，" }, { "name": "italic", "data": [ { "name": "text", "data": "S" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "b" } ] }, { "name": "text", "data": "是10个空白溶液的标准偏差，" }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "表示校准曲线的斜率)，计算出检测限为0.59 μmol/L。以上结果表明，利用1可以在水溶液中实现对Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "的定量检测。" } ] }, { "name": "fig", "data": { "id": "F9", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图9" } ], "title": [ { "name": "text", "data": "不同Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "离子浓度下，化合物1在482 nm处的荧光信号变化。条件：[1]＝10 μmol/L，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "＝344 nm。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.9" } ], "title": [ { "name": "text", "data": "Fluorescence signal of 1 at 482 nm as a function of Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": " concentration. Conditions: [1]＝10 μmol/L," }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "＝344 nm." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348682&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348686&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348684&type=" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4　结论" } ], "level": "1", "id": "s4" } }, { "name": "p", "data": [ { "name": "text", "data": "本文制备了一种新型的有机无机复合AIE分子三苯乙烯炔金-三苯基膦(1)。该物质合成简单，成本低廉。在聚集态中或固态时，1表现出强烈的蓝色荧光，具有明显的AIE特征。机理研究表明，化合物1的AIE特性来自于限制分子内旋转机理。进一步，利用化合物1可以实现对水溶液中Hg" }, { "name": "sup", "data": [ { "name": "text", "data": "2＋" } ] }, { "name": "text", "data": "的选择性定量检测，检测限达到0.59 μmol/L。" } ] } ] } ], "footnote": [], "reflist": { "title": [ { "name": "text", "data": "参考文献：" } ], "data": [ { "id": "R1", "label": "[1]", "citation": [ { "lang": "zh", "text": [ { "name": "text", "data": "ZHOU N" }, { "name": "text", "data": ", " }, { "name": "text", "data": "HUO F J" }, { "name": "text", "data": ", " }, { "name": "text", "data": "YUE Y K" }, { "name": "text", "data": ", " }, { "name": "text", "data": "et al" }, { "name": "text", "data": ". 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