本文主要研究内容
作者雷娜娜（2019）在《基于稀土杂多酸盐或配合物与表面活性剂的发光有序分子聚集体的组装和性质研究》一文中研究指出：基于自身特殊的电子构型及丰富的4f电子层轨道,稀土离子具有优异的光物理性质,如线状光谱、激发态寿命长、Stokes位移大及发射谱线范围宽(从可见到近红外光区)等。而稀土杂多酸盐或配合物因天线效应的存在,具有显著增强的荧光性能,可作为理想的发光基元。近年来,通过非共价相互作用力,将稀土发光基元共组装到有序分子聚集体基质中,可有效改善其发光性能、光热稳定性及可加工性。并且,利用有序分子聚集体丰富可调的聚集形态、灵敏的环境刺激响应性及易于加工处理等优势,结合稀土发光基元的光物理性质对其周围微化学环境的敏感性,有望制备智能型稀土发光软聚集体或具有一定检测性能的有序膜材料。此外,作为一类新兴非水溶剂,离子液体逐渐被开发为有序分子聚集体的良好组装介质;同时,也可作为稀土发光基元的理想分散溶剂。因此,设计构筑离子液体参与的稀土发光有序分子聚集体,将有望得到兼具稳定性和增强发光性能的稀土发光软材料,并拓展有序发光材料的设计范围。这对拓展离子液体及其有序分子聚集体的功能化应用也具有重要意义。本论文以稀土杂多酸盐或配合物为发光基元,利用其与表面活性剂共组装的策略,构筑了一系列响应型稀土发光增强的有序分子聚集体;并以离子液体参与的溶致液晶为基质,成功构筑了包括白色荧光的全色可调液晶软材料;又通过合理设计可聚合型溶致液晶基质,采用原位光聚合策略制备了有序的多色荧光膜材料。通过系统考察有序分子聚集体基质对稀土发光性能的影响规律,探索了增强其光物理性质的途径。论文主要开展了以下五个方面的工作:一、选取具有pH依赖质子化行为的两性表面活性剂(十四烷基二甲基氧化胺,C14DMAO)和Na9EuW10O36·32H2O(EuW10)阴离子簇,通过调节C14DMAO/EuW10摩尔比(R),系统考察了二者在水溶液中的共组装行为及荧光性能变化。在PR=20时,得到了稳定性能较好的荧光增强纳米带。研究表明,纳米带具有沿轴向排列的有序层状结构,这在杂多酸盐自组装体系中是很少见的。而C14DMAO在体系pH值为6.5时的部分质子化是纳米带形成的关键。因纳米带中能较好地屏蔽EuW10周围的水分子,其荧光强度、寿命及绝对量子产率得到极大的提高。此外,C14DMAO的pH可逆质子化行为也赋予了该纳米带灵敏的pH刺激响应性。因此,该C14DMAO/EuW10共组装纳米带的成功构筑,不仅丰富了杂多酸盐有序分子聚集体的形态,而且为pH响应智能材料的设计提供了有价值的参考。二、以具有酶响应性的阳离子型表面活性剂----氯化肉豆蔻酰胆碱(Myr)和EuW10阴离子簇为共组装构筑基元,通过合理调控Myr/EuW10摩尔比值为36(电荷比值为4)时,得到了稳定性能好、发光性能明显增强的多层超分子球形聚集体。研究发现,聚集体结构中过量的Myr分子以亲水头基朝外的方式排列在超分子球表层,使其能稳定分散在水溶液中。同时,基于Myr的酶响应性及EuW10的荧光性能对其微化学环境的敏感性,制备得到的超分子球对pH、Cu2+/Fe3+及酶均表现出刺激响应性能。本工作不仅为杂多酸盐/阳离子型表面活性剂共组装体系聚集行为的研究提供了新的内容,同时是拓展其生物相容体系应用的有益尝试。三、利用阳离子型表面活性剂----1-十八烷基-3-甲基咪唑溴盐([C18mim]Br)与EuW10在等电荷比例下的静电作用,得到了表面活性剂包覆的EuW10复合物(SEP)。SEP进一步在质子性离子液体----硝酸乙基铵(EAN)中组装形成粘弹性的发光软材料,其聚集体为具有层状结构的微米带。在氢键及疏溶剂作用力驱动下,SEP在EAN中组装时,其外围的表面活性剂重排并采取交叉双层排列,EuW10阴离子作为反离子吸附在[C18mim]Br双分子层表面的咪唑头基附近。由于[C18mim]Br对EuW10纳米簇的有效隔离和束缚,SEP的非辐射振动失活大大减弱,其荧光寿命及量子效率相应提高。同时,选择EAN作为组装介质能从根本上避免水分子配位导致的荧光猝灭,从而改善最终软聚集体的发光性能。因此,SEP及相应的软聚集体的荧光性能可以比拟文献报道的含EuW10的固体材料。此外,作为对SEP在离子液体中聚集行为的首次探讨,本工作为相关领域的研究提供了有价值的参考。四、以两亲嵌段共聚物Pluronic P123与离子液体(1-丁基-3-甲基-咪唑六氟磷酸盐)构建的溶致液晶为基质,通过巧妙地共掺杂吡啶二甲酸稀土配合物(Ln-DPA)和聚集诱导发光化合物----四(5-羟基苯基)乙烷(TPE-OH)到液晶中,我们建立了一种便捷且通用的策略来制备多色及白色荧光液晶软材料。对其光物理性质的分析表明,离子液体参与构筑的液晶基质能有效束缚并隔离发光基元。因此,Eu-DPA配合物掺杂的液晶呈现目前报道的吡啶二甲酸稀土配合物杂化材料中最长的荧光寿命,甚至高于其介孔固体材料。同时,由于TPE-OH分子构象的固定,其掺杂的液晶具有优于相应离子液体溶液的荧光性能。通过准确调节三原色发光基元在液晶基质中的掺杂比例,得到了包括CIE色度坐标为(0.328,0.315)白色荧光的系列荧光颜色。此外,由于TPE-OH与Ln-DPA不同的激发光谱,通过切换激发波长从254到365 nm,能可逆有效地调控液晶荧光从白色变为蓝色。此液晶材料形状易于加工处理,便于光学器件的应用,这为后续高效荧光软材料的制备提供了思路。五、通过合理设计可聚合型层状溶致液晶的基质,选择适宜的Ln-DPA作为多色荧光基元掺杂其中,利用原位光聚合的策略,制备得到了多色发光有序薄膜。研究表明,膜基质的层状纳米结构对Eu-DPA的均匀分散和隔离效应,及较密实的聚合物链通过静电和氢键作用对配合物的束缚作用,均能有效地减弱配合物的非辐射跃迁驰豫和自猝灭过程,从而保证膜材料优异的发光性能。因此,与相应的Eu-DPA水溶液、固体粉末及溶致液晶相比,Eu-DPA掺杂薄膜具有增强的荧光性能,甚至可与其固体介孔硅发光材料相媲美。除了优异的多色发光性能,该薄膜同时具备一定的热稳定性、力学强度、及对于较宽pH范围和多种金属离子水溶液的刺激稳定性。这为兼具优异荧光性能和稳定性的多色稀土发光有序膜的构筑提供了有价值的理论参考。
Abstract
ji yu zi shen te shu de dian zi gou xing ji feng fu de 4fdian zi ceng gui dao ,xi tu li zi ju you you yi de guang wu li xing zhi ,ru xian zhuang guang pu 、ji fa tai shou ming chang 、Stokeswei yi da ji fa she pu xian fan wei kuan (cong ke jian dao jin gong wai guang ou )deng 。er xi tu za duo suan yan huo pei ge wu yin tian xian xiao ying de cun zai ,ju you xian zhe zeng jiang de ying guang xing neng ,ke zuo wei li xiang de fa guang ji yuan 。jin nian lai ,tong guo fei gong jia xiang hu zuo yong li ,jiang xi tu fa guang ji yuan gong zu zhuang dao you xu fen zi ju ji ti ji zhi zhong ,ke you xiao gai shan ji fa guang xing neng 、guang re wen ding xing ji ke jia gong xing 。bing ju ,li yong you xu fen zi ju ji ti feng fu ke diao de ju ji xing tai 、ling min de huan jing ci ji xiang ying xing ji yi yu jia gong chu li deng you shi ,jie ge xi tu fa guang ji yuan de guang wu li xing zhi dui ji zhou wei wei hua xue huan jing de min gan xing ,you wang zhi bei zhi neng xing xi tu fa guang ruan ju ji ti huo ju you yi ding jian ce xing neng de you xu mo cai liao 。ci wai ,zuo wei yi lei xin xing fei shui rong ji ,li zi ye ti zhu jian bei kai fa wei you xu fen zi ju ji ti de liang hao zu zhuang jie zhi ;tong shi ,ye ke zuo wei xi tu fa guang ji yuan de li xiang fen san rong ji 。yin ci ,she ji gou zhu li zi ye ti can yu de xi tu fa guang you xu fen zi ju ji ti ,jiang you wang de dao jian ju wen ding xing he zeng jiang fa guang xing neng de xi tu fa guang ruan cai liao ,bing ta zhan you xu fa guang cai liao de she ji fan wei 。zhe dui ta zhan li zi ye ti ji ji you xu fen zi ju ji ti de gong neng hua ying yong ye ju you chong yao yi yi 。ben lun wen yi xi tu za duo suan yan huo pei ge wu wei fa guang ji yuan ,li yong ji yu biao mian huo xing ji gong zu zhuang de ce lve ,gou zhu le yi ji lie xiang ying xing xi tu fa guang zeng jiang de you xu fen zi ju ji ti ;bing yi li zi ye ti can yu de rong zhi ye jing wei ji zhi ,cheng gong gou zhu le bao gua bai se ying guang de quan se ke diao ye jing ruan cai liao ;you tong guo ge li she ji ke ju ge xing rong zhi ye jing ji zhi ,cai yong yuan wei guang ju ge ce lve zhi bei le you xu de duo se ying guang mo cai liao 。tong guo ji tong kao cha you xu fen zi ju ji ti ji zhi dui xi tu fa guang xing neng de ying xiang gui lv ,tan suo le zeng jiang ji guang wu li xing zhi de tu jing 。lun wen zhu yao kai zhan le yi xia wu ge fang mian de gong zuo :yi 、shua qu ju you pHyi lai zhi zi hua hang wei de liang xing biao mian huo xing ji (shi si wan ji er jia ji yang hua an ,C14DMAO)he Na9EuW10O36·32H2O(EuW10)yin li zi cu ,tong guo diao jie C14DMAO/EuW10ma er bi (R),ji tong kao cha le er zhe zai shui rong ye zhong de gong zu zhuang hang wei ji ying guang xing neng bian hua 。zai PR=20shi ,de dao le wen ding xing neng jiao hao de ying guang zeng jiang na mi dai 。yan jiu biao ming ,na mi dai ju you yan zhou xiang pai lie de you xu ceng zhuang jie gou ,zhe zai za duo suan yan zi zu zhuang ti ji zhong shi hen shao jian de 。er C14DMAOzai ti ji pHzhi wei 6.5shi de bu fen zhi zi hua shi na mi dai xing cheng de guan jian 。yin na mi dai zhong neng jiao hao de bing bi EuW10zhou wei de shui fen zi ,ji ying guang jiang du 、shou ming ji jue dui liang zi chan lv de dao ji da de di gao 。ci wai ,C14DMAOde pHke ni zhi zi hua hang wei ye fu yu le gai na mi dai ling min de pHci ji xiang ying xing 。yin ci ,gai C14DMAO/EuW10gong zu zhuang na mi dai de cheng gong gou zhu ,bu jin feng fu le za duo suan yan you xu fen zi ju ji ti de xing tai ,er ju wei pHxiang ying zhi neng cai liao de she ji di gong le you jia zhi de can kao 。er 、yi ju you mei xiang ying xing de yang li zi xing biao mian huo xing ji ----lv hua rou dou kou xian dan jian (Myr)he EuW10yin li zi cu wei gong zu zhuang gou zhu ji yuan ,tong guo ge li diao kong Myr/EuW10ma er bi zhi wei 36(dian he bi zhi wei 4)shi ,de dao le wen ding xing neng hao 、fa guang xing neng ming xian zeng jiang de duo ceng chao fen zi qiu xing ju ji ti 。yan jiu fa xian ,ju ji ti jie gou zhong guo liang de Myrfen zi yi qin shui tou ji chao wai de fang shi pai lie zai chao fen zi qiu biao ceng ,shi ji neng wen ding fen san zai shui rong ye zhong 。tong shi ,ji yu Myrde mei xiang ying xing ji EuW10de ying guang xing neng dui ji wei hua xue huan jing de min gan xing ,zhi bei de dao de chao fen zi qiu dui pH、Cu2+/Fe3+ji mei jun biao xian chu ci ji xiang ying xing neng 。ben gong zuo bu jin wei za duo suan yan /yang li zi xing biao mian huo xing ji gong zu zhuang ti ji ju ji hang wei de yan jiu di gong le xin de nei rong ,tong shi shi ta zhan ji sheng wu xiang rong ti ji ying yong de you yi chang shi 。san 、li yong yang li zi xing biao mian huo xing ji ----1-shi ba wan ji -3-jia ji mi zuo xiu yan ([C18mim]Br)yu EuW10zai deng dian he bi li xia de jing dian zuo yong ,de dao le biao mian huo xing ji bao fu de EuW10fu ge wu (SEP)。SEPjin yi bu zai zhi zi xing li zi ye ti ----xiao suan yi ji an (EAN)zhong zu zhuang xing cheng nian dan xing de fa guang ruan cai liao ,ji ju ji ti wei ju you ceng zhuang jie gou de wei mi dai 。zai qing jian ji shu rong ji zuo yong li qu dong xia ,SEPzai EANzhong zu zhuang shi ,ji wai wei de biao mian huo xing ji chong pai bing cai qu jiao cha shuang ceng pai lie ,EuW10yin li zi zuo wei fan li zi xi fu zai [C18mim]Brshuang fen zi ceng biao mian de mi zuo tou ji fu jin 。you yu [C18mim]Brdui EuW10na mi cu de you xiao ge li he shu fu ,SEPde fei fu she zhen dong shi huo da da jian ruo ,ji ying guang shou ming ji liang zi xiao lv xiang ying di gao 。tong shi ,shua ze EANzuo wei zu zhuang jie zhi neng cong gen ben shang bi mian shui fen zi pei wei dao zhi de ying guang cu mie ,cong er gai shan zui zhong ruan ju ji ti de fa guang xing neng 。yin ci ,SEPji xiang ying de ruan ju ji ti de ying guang xing neng ke yi bi ni wen suo bao dao de han EuW10de gu ti cai liao 。ci wai ,zuo wei dui SEPzai li zi ye ti zhong ju ji hang wei de shou ci tan tao ,ben gong zuo wei xiang guan ling yu de yan jiu di gong le you jia zhi de can kao 。si 、yi liang qin qian duan gong ju wu Pluronic P123yu li zi ye ti (1-ding ji -3-jia ji -mi zuo liu fu lin suan yan )gou jian de rong zhi ye jing wei ji zhi ,tong guo qiao miao de gong can za bi ding er jia suan xi tu pei ge wu (Ln-DPA)he ju ji you dao fa guang hua ge wu ----si (5-qiang ji ben ji )yi wan (TPE-OH)dao ye jing zhong ,wo men jian li le yi chong bian jie ju tong yong de ce lve lai zhi bei duo se ji bai se ying guang ye jing ruan cai liao 。dui ji guang wu li xing zhi de fen xi biao ming ,li zi ye ti can yu gou zhu de ye jing ji zhi neng you xiao shu fu bing ge li fa guang ji yuan 。yin ci ,Eu-DPApei ge wu can za de ye jing cheng xian mu qian bao dao de bi ding er jia suan xi tu pei ge wu za hua cai liao zhong zui chang de ying guang shou ming ,shen zhi gao yu ji jie kong gu ti cai liao 。tong shi ,you yu TPE-OHfen zi gou xiang de gu ding ,ji can za de ye jing ju you you yu xiang ying li zi ye ti rong ye de ying guang xing neng 。tong guo zhun que diao jie san yuan se fa guang ji yuan zai ye jing ji zhi zhong de can za bi li ,de dao le bao gua CIEse du zuo biao wei (0.328,0.315)bai se ying guang de ji lie ying guang yan se 。ci wai ,you yu TPE-OHyu Ln-DPAbu tong de ji fa guang pu ,tong guo qie huan ji fa bo chang cong 254dao 365 nm,neng ke ni you xiao de diao kong ye jing ying guang cong bai se bian wei lan se 。ci ye jing cai liao xing zhuang yi yu jia gong chu li ,bian yu guang xue qi jian de ying yong ,zhe wei hou xu gao xiao ying guang ruan cai liao de zhi bei di gong le sai lu 。wu 、tong guo ge li she ji ke ju ge xing ceng zhuang rong zhi ye jing de ji zhi ,shua ze kuo yi de Ln-DPAzuo wei duo se ying guang ji yuan can za ji zhong ,li yong yuan wei guang ju ge de ce lve ,zhi bei de dao le duo se fa guang you xu bao mo 。yan jiu biao ming ,mo ji zhi de ceng zhuang na mi jie gou dui Eu-DPAde jun yun fen san he ge li xiao ying ,ji jiao mi shi de ju ge wu lian tong guo jing dian he qing jian zuo yong dui pei ge wu de shu fu zuo yong ,jun neng you xiao de jian ruo pei ge wu de fei fu she yue qian chi yu he zi cu mie guo cheng ,cong er bao zheng mo cai liao you yi de fa guang xing neng 。yin ci ,yu xiang ying de Eu-DPAshui rong ye 、gu ti fen mo ji rong zhi ye jing xiang bi ,Eu-DPAcan za bao mo ju you zeng jiang de ying guang xing neng ,shen zhi ke yu ji gu ti jie kong gui fa guang cai liao xiang pi mei 。chu le you yi de duo se fa guang xing neng ,gai bao mo tong shi ju bei yi ding de re wen ding xing 、li xue jiang du 、ji dui yu jiao kuan pHfan wei he duo chong jin shu li zi shui rong ye de ci ji wen ding xing 。zhe wei jian ju you yi ying guang xing neng he wen ding xing de duo se xi tu fa guang you xu mo de gou zhu di gong le you jia zhi de li lun can kao 。
论文参考文献
论文详细介绍
论文作者分别是来自山东大学的雷娜娜，发表于刊物山东大学2019-07-16论文，是一篇关于稀土论文,荧光论文,表面活性剂论文,有序分子聚集体论文,离子液体论文,山东大学2019-07-16论文的文章。本文可供学术参考使用，各位学者可以免费参考阅读下载，文章观点不代表本站观点，资料来自山东大学2019-07-16论文网站，若本站收录的文献无意侵犯了您的著作版权，请联系我们删除。
标签：稀土论文; 荧光论文; 表面活性剂论文; 有序分子聚集体论文; 离子液体论文; 山东大学2019-07-16论文;