本文主要研究内容
作者夏体锋（2019）在《基于六核簇稀土-有机框架材料的构筑及荧光传感应用》一文中研究指出：稀土-有机框架材料(Lanthanide metal-organic frameworks,简称Ln-MOFs)是近二十年来新兴的一类有机-无机杂化多孔晶态材料,由于其独特的发光特性、丰富的发光中心和多变的可设计性,在荧光传感、生物成像、白光发射和显示照明等领域展现出广阔的应用前景。但是由于稀土离子成键方向性不强、配位模式多样,Ln-MOFs的结构可预测性较差、可控制备困难。针对以上难题,本文提出了核簇基的构筑策略,设计合成了一系列同构的六核簇Ln-MOFs,通过功能位点引入、孔道结构延伸和电子能级调控等实现了神经疾病标记物谷氨酸、还原性辅酶NADP、氧气和生理温度、有机溶剂中的痕量水、三硝基苯酚的高灵敏度荧光检测。并通过喷墨打印和印章的方式实现了 Ln-MOFs荧光防伪图案制备,把Ln-MOFs与光纤进行整合搭建了一个便携式光纤(?)Ln-MOFs荧光传感器,为发光Ln-MOFs材料实现器件化应用提供了新思路。以邻氟苯甲酸为核簇导向剂,选用含羟基的有机配体H2BDC-OH与稀土盐通过核簇基的构筑策略合成了一类多孔六核簇Ln-MOFs材料Ln(BDC-OH)。Ln(BDC-OH)是由六核稀土簇[Ln6(μ3-OH)8(O2C-)12]与周围十二个H2BDC-OH连接形成的三维框架材料,该框架中含有半径分别为3.4 A和4.9 A的四面体和八面体两种孔笼,BET面积为767.8 m2·g-1。以配体的发光为检测信号,稀土离子发光为参比内标,Ln(BDC-OH)(Ln=Eu、Tb)悬浮液实现了神经疾病标记物G lu的内标法和比色型检测。该探针具有良好的抗干扰性、重复性和生物相容性,工作区间覆盖了Glu的正常生理浓度范围。基于配体和稀土离子的发光,设计了一个一对二的解码器逻辑门,可用于人体内Glu浓度的监控和神经疾病的预防。采用联苯二羧酸线性配体H2BPDC-xN(x=0,1,2)进行取代,通过核簇基构筑策略制备得到三个同构的Ln-MOFs材料Ln(BPDC-xN)(Ln=Eu/Tb,x=0,1,2),实现了六核簇Ln-MOFs材料的孔笼调控。孔笼尺寸的增长降低了框架材料的稳定性,使得NADP分子能有效破坏这三个材料的框架结构并打断配体向稀土离子的敏化,从而实现NADP的选择性荧光检测。氮功能位点的引入能吸引和驱动NADP分子向探针周围富集,提高检测灵敏度,这三个框架材料对NADP的检测限分别为1.36 μM、0.84 μM和0.43 μM。Ln(BPDC-xN)(Ln=Eu/Tb,x=0,1,2)对NADP的检测选择性好,细胞环境中的主要物质和类似物NAD对检测几乎没有干扰。核簇基的构筑策略有利于对Ln-MOFs材料的能级结构和能量传递过程进行调节,采用三重态能级较低的1,4-H2NDC为有机配体,制备得到了具有能量回传特性的六核簇Ln-MOFs材料Eu(1,4-NDC)。基于适当的Eu3+离子向配体的能量回传特性,Eu(1,4-NDC)实现了快速高效的氧气荧光检测,荧光淬灭常数Ksv为13.3 bar-1、检测限低至0.021%,荧光响应和恢复时间分别为10秒和70秒。进一步采用Eu3+/Gd3+共掺策略对能量回传效率进行提高,实现了高灵敏的生理温度传感。Eu3+/Gd3+共掺的EuxGdi-x(1,4-NDC)(x=0.0005、0.001、0.003、0.01)中Eu3+发光比Eu(1,4-NDC)对温度更灵敏,且同时存在对温度不敏感的第二发光中心,实现了生理温度的单一发射模式、双发射模式和比色型模式三通道检测。EuxGdi-x(1,4-NDC)(x=0.0005、0.001、0.003、0.01)的最大相对灵敏度均位于生理温度范闱内,且在整个生理温度区间,单模式柃测时的相对灵敏度均在4.00%℃-1以上,双模式检测时的相对灵敏度均在3.00%℃-1以上,是一种性能优异的荧光温度探针。采用对水分子具有氢键作用和荧光响应的H2BDC-NH2为有机配体,与稀土盐合成了一类多孔六核簇 Ln-MOFs 材料 Ln(BDC-NH2)。Ln(BDC-NH2)(Ln=Eu、Tb)在水中具有合适的溶度积,未溶解部分能保持晶体孔道的完整性。基于配体的溶出、水的淬灭效应和能量回传共同作用,实现了多种有机溶剂中痕量水的比率型和比色型检测,在THF中检测限分别为0.002 vol%和0.001 vol%。通过印章和喷墨打印的方式把Eu(BDC-NH2)制备成荧光防伪图案,该荧光防伪图案可通过水/水蒸气处理进行读取。针对三硝基苯酚(PA)的缺电子特性,把富电子的蒽环引入到荧光探针Eu(1,4-NDC)中以提高检测灵敏度和选择性。基于光诱导电子转移和自吸收的协同作用,Eu(1,4-NDC)对PA具有优异的荧光检测性能,淬灭常数Ksv=3.22X 104 M-1,检测限低达37.6 ppb,且检测不受其他相似硝基化合物的干扰。进一步把Eu(1,4-NDC)与水凝胶光纤进行整合,搭建了一个光纤(?)MOFs荧光传感平台。水凝胶光纤(?)Eu(1,4-NDC)荧光传感器对PA的检测具有更高的荧光淬灭常数(6.13 × 104 M-1),并成功应用于真实水样中的PA检测,为发光MOFs探针器件化应用提供了指导。
Abstract
xi tu -you ji kuang jia cai liao (Lanthanide metal-organic frameworks,jian chen Ln-MOFs)shi jin er shi nian lai xin xing de yi lei you ji -mo ji za hua duo kong jing tai cai liao ,you yu ji du te de fa guang te xing 、feng fu de fa guang zhong xin he duo bian de ke she ji xing ,zai ying guang chuan gan 、sheng wu cheng xiang 、bai guang fa she he xian shi zhao ming deng ling yu zhan xian chu an kuo de ying yong qian jing 。dan shi you yu xi tu li zi cheng jian fang xiang xing bu jiang 、pei wei mo shi duo yang ,Ln-MOFsde jie gou ke yu ce xing jiao cha 、ke kong zhi bei kun nan 。zhen dui yi shang nan ti ,ben wen di chu le he cu ji de gou zhu ce lve ,she ji ge cheng le yi ji lie tong gou de liu he cu Ln-MOFs,tong guo gong neng wei dian yin ru 、kong dao jie gou yan shen he dian zi neng ji diao kong deng shi xian le shen jing ji bing biao ji wu gu an suan 、hai yuan xing fu mei NADP、yang qi he sheng li wen du 、you ji rong ji zhong de hen liang shui 、san xiao ji ben fen de gao ling min du ying guang jian ce 。bing tong guo pen mo da yin he yin zhang de fang shi shi xian le Ln-MOFsying guang fang wei tu an zhi bei ,ba Ln-MOFsyu guang qian jin hang zheng ge da jian le yi ge bian xie shi guang qian (?)Ln-MOFsying guang chuan gan qi ,wei fa guang Ln-MOFscai liao shi xian qi jian hua ying yong di gong le xin sai lu 。yi lin fu ben jia suan wei he cu dao xiang ji ,shua yong han qiang ji de you ji pei ti H2BDC-OHyu xi tu yan tong guo he cu ji de gou zhu ce lve ge cheng le yi lei duo kong liu he cu Ln-MOFscai liao Ln(BDC-OH)。Ln(BDC-OH)shi you liu he xi tu cu [Ln6(μ3-OH)8(O2C-)12]yu zhou wei shi er ge H2BDC-OHlian jie xing cheng de san wei kuang jia cai liao ,gai kuang jia zhong han you ban jing fen bie wei 3.4 Ahe 4.9 Ade si mian ti he ba mian ti liang chong kong long ,BETmian ji wei 767.8 m2·g-1。yi pei ti de fa guang wei jian ce xin hao ,xi tu li zi fa guang wei can bi nei biao ,Ln(BDC-OH)(Ln=Eu、Tb)xuan fu ye shi xian le shen jing ji bing biao ji wu G lude nei biao fa he bi se xing jian ce 。gai tan zhen ju you liang hao de kang gan rao xing 、chong fu xing he sheng wu xiang rong xing ,gong zuo ou jian fu gai le Glude zheng chang sheng li nong du fan wei 。ji yu pei ti he xi tu li zi de fa guang ,she ji le yi ge yi dui er de jie ma qi luo ji men ,ke yong yu ren ti nei Glunong du de jian kong he shen jing ji bing de yu fang 。cai yong lian ben er suo suan xian xing pei ti H2BPDC-xN(x=0,1,2)jin hang qu dai ,tong guo he cu ji gou zhu ce lve zhi bei de dao san ge tong gou de Ln-MOFscai liao Ln(BPDC-xN)(Ln=Eu/Tb,x=0,1,2),shi xian le liu he cu Ln-MOFscai liao de kong long diao kong 。kong long che cun de zeng chang jiang di le kuang jia cai liao de wen ding xing ,shi de NADPfen zi neng you xiao po huai zhe san ge cai liao de kuang jia jie gou bing da duan pei ti xiang xi tu li zi de min hua ,cong er shi xian NADPde shua ze xing ying guang jian ce 。dan gong neng wei dian de yin ru neng xi yin he qu dong NADPfen zi xiang tan zhen zhou wei fu ji ,di gao jian ce ling min du ,zhe san ge kuang jia cai liao dui NADPde jian ce xian fen bie wei 1.36 μM、0.84 μMhe 0.43 μM。Ln(BPDC-xN)(Ln=Eu/Tb,x=0,1,2)dui NADPde jian ce shua ze xing hao ,xi bao huan jing zhong de zhu yao wu zhi he lei shi wu NADdui jian ce ji hu mei you gan rao 。he cu ji de gou zhu ce lve you li yu dui Ln-MOFscai liao de neng ji jie gou he neng liang chuan di guo cheng jin hang diao jie ,cai yong san chong tai neng ji jiao di de 1,4-H2NDCwei you ji pei ti ,zhi bei de dao le ju you neng liang hui chuan te xing de liu he cu Ln-MOFscai liao Eu(1,4-NDC)。ji yu kuo dang de Eu3+li zi xiang pei ti de neng liang hui chuan te xing ,Eu(1,4-NDC)shi xian le kuai su gao xiao de yang qi ying guang jian ce ,ying guang cui mie chang shu Ksvwei 13.3 bar-1、jian ce xian di zhi 0.021%,ying guang xiang ying he hui fu shi jian fen bie wei 10miao he 70miao 。jin yi bu cai yong Eu3+/Gd3+gong can ce lve dui neng liang hui chuan xiao lv jin hang di gao ,shi xian le gao ling min de sheng li wen du chuan gan 。Eu3+/Gd3+gong can de EuxGdi-x(1,4-NDC)(x=0.0005、0.001、0.003、0.01)zhong Eu3+fa guang bi Eu(1,4-NDC)dui wen du geng ling min ,ju tong shi cun zai dui wen du bu min gan de di er fa guang zhong xin ,shi xian le sheng li wen du de chan yi fa she mo shi 、shuang fa she mo shi he bi se xing mo shi san tong dao jian ce 。EuxGdi-x(1,4-NDC)(x=0.0005、0.001、0.003、0.01)de zui da xiang dui ling min du jun wei yu sheng li wen du fan wei nei ,ju zai zheng ge sheng li wen du ou jian ,chan mo shi ling ce shi de xiang dui ling min du jun zai 4.00%℃-1yi shang ,shuang mo shi jian ce shi de xiang dui ling min du jun zai 3.00%℃-1yi shang ,shi yi chong xing neng you yi de ying guang wen du tan zhen 。cai yong dui shui fen zi ju you qing jian zuo yong he ying guang xiang ying de H2BDC-NH2wei you ji pei ti ,yu xi tu yan ge cheng le yi lei duo kong liu he cu Ln-MOFs cai liao Ln(BDC-NH2)。Ln(BDC-NH2)(Ln=Eu、Tb)zai shui zhong ju you ge kuo de rong du ji ,wei rong jie bu fen neng bao chi jing ti kong dao de wan zheng xing 。ji yu pei ti de rong chu 、shui de cui mie xiao ying he neng liang hui chuan gong tong zuo yong ,shi xian le duo chong you ji rong ji zhong hen liang shui de bi lv xing he bi se xing jian ce ,zai THFzhong jian ce xian fen bie wei 0.002 vol%he 0.001 vol%。tong guo yin zhang he pen mo da yin de fang shi ba Eu(BDC-NH2)zhi bei cheng ying guang fang wei tu an ,gai ying guang fang wei tu an ke tong guo shui /shui zheng qi chu li jin hang dou qu 。zhen dui san xiao ji ben fen (PA)de que dian zi te xing ,ba fu dian zi de en huan yin ru dao ying guang tan zhen Eu(1,4-NDC)zhong yi di gao jian ce ling min du he shua ze xing 。ji yu guang you dao dian zi zhuai yi he zi xi shou de xie tong zuo yong ,Eu(1,4-NDC)dui PAju you you yi de ying guang jian ce xing neng ,cui mie chang shu Ksv=3.22X 104 M-1,jian ce xian di da 37.6 ppb,ju jian ce bu shou ji ta xiang shi xiao ji hua ge wu de gan rao 。jin yi bu ba Eu(1,4-NDC)yu shui ning jiao guang qian jin hang zheng ge ,da jian le yi ge guang qian (?)MOFsying guang chuan gan ping tai 。shui ning jiao guang qian (?)Eu(1,4-NDC)ying guang chuan gan qi dui PAde jian ce ju you geng gao de ying guang cui mie chang shu (6.13 × 104 M-1),bing cheng gong ying yong yu zhen shi shui yang zhong de PAjian ce ,wei fa guang MOFstan zhen qi jian hua ying yong di gong le zhi dao 。
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论文作者分别是来自浙江大学的夏体锋，发表于刊物浙江大学2019-07-04论文，是一篇关于稀土有机框架材料论文,稀土簇论文,荧光检测论文,同构设计论文,器件化论文,溶度积论文,浙江大学2019-07-04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，资料来自浙江大学2019-07-04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。
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