标题: 奈米粒子应用于NAD(P)H: 醌氧化还原酶1、银离子与镉离子检测
Applications of Nanoparticles for NAD(P)H: quinone oxidoreductase isozyme 1, Ag+ and Cd2+ Detection
作者: 宋益铭
Sung, Yi-Ming
吴淑褓
Wu, Shu-Pao
应用化学系硕博士班
关键字: 奈米粒子;NAD(P)H: 醌氧化还原酶1;银离子;镉离子;掺杂锰离子硫化锌量子点;金奈米粒子;Nanoparticles;NAD(P)H: quinone oxidoreductase isozyme 1;Silver ion;Cadmium ion;Mn-Doped ZnS Quantum Dots;Gold nanoparticles
公开日期: 2013
摘要: (一) 醌修饰之掺杂锰离子硫化锌量子点为NAD(P)H: 醌氧化还原酶1感测探针
在掺杂锰离子硫化锌量子点(ZnS(Mn2+) QDs)表面修饰醌衍生物,使磷光淬息,得到NAD(P)H: 醌氧化还原酶1 (NQO1) 感测探针(Q-ZnS(Mn2+) QDs)。探针表面上的醌衍生物与NQO1反应,被还原成氢醌后,从探针表面离去,中止光诱导电子转移 (photo-induced electron transfer, PET),启动磷光放射机制,以侦测NQO1的存在。从NQO1酵素动力学实验结果,显示NQO1对Q-ZnS(Mn2+) QDs有良好的反应活性,并可从磷光生成速率定量NQO1的浓度。Q-ZnS(Mn2+) QDs对于细胞有极低的生物毒性,可用于NQO1表现过量的细胞显影实验,并检测出NQO1表现于细胞质与细胞核。成功发展了一个具有高选择性与高灵敏度的NQO1感测探针,可用于侦测NQO1表现过量的人类肿瘤细胞。
(二) 腺嘌呤修饰之金奈米粒子应用于银离子检测
设计金奈米粒子表面修饰腺嘌呤衍生物(N-1-(2-mercaptoethyl)adenine),做为银离子的感测探针(MEA-AuNPs)。MEA-AuNPs对银离子检测有专一性,银离子会导致MEA-AuNPs聚集,使金奈米水溶液的颜色从酒红色转变成蓝紫色。MEA-AuNPs检测银离子适用于pH 6-9的水溶液,其侦测极限为 3.3 nM。从核磁共振光谱可以得知银离子与腺嘌呤(adenine)有良好的交互作用,使得MEA-AuNPs对于银离子检测有优异的选择性与高灵敏。MEA-AuNPs的银离子检验,不会受到其他金属离子的影响,可用于真实湖水中的微量银离子检测,得回收率为95.3-103.5% ,因此MEA-AuNPs可适用于复杂环境的微量银离子检测应用。
(三) 二吡咯甲硫酮修饰之金奈米粒子为高灵敏镉离子感测探针
二吡咯甲硫酮修饰金奈米粒子(DP-AuNPs)是一个新型高灵敏度与专一性的镉离子感测探针。在含有镉离子的样品中,DP-AuNPs发生聚集现象,金奈米水溶液颜色,从酒红色转变成蓝紫色,从紫外-可见光光谱图可知吸收峰从波长520 nm红位移至波长 635 nm,其侦测极限达至16.6 nM。DP-AuNPs对镉离子有专一性。DP-AuNPs对于镉离子有很好的配位能力,不会受到其他金属离子的影响,所以适用于复杂的水溶液样品检测镉离子,其适合侦测pH范围为4-9.5的水溶液中,可用于检测真实湖水样品微量镉离子,并展现其良好检测结果。
(1) Quinone modified Mn-Doped ZnS Quantum Dots for Room Temperature Phosphorescence sensing of NQO1
A new room-temperature phosphorescence NAD(P)H: quinone oxidoreductase isozyme 1 (NQO1) sensor was developed by using quinone-modified Mn-doped ZnS quantum dots (Q-ZnS(Mn2+) QDs). It can selectively detect NQO1 in vitro and vivo through phosphorescence generated by reduction-initiated removal of quinones on its surface with NQO1. Enzyme kinetics of NQO1 was measured by phosphorescence enhancement of Q-ZnS(Mn2+) QDs revealed its highly catalytic activity towards Q-ZnS(Mn2+) QDs. High viability of cells in presence of Q-ZnS(Mn2+) QDs showed the low cytotoxicity to A549 cells from MTT assay. Therefore, Q-ZnS(Mn2+) QDs can be applied to detect NQO1 which is overexpressed in cytoplasma and nucleus of cancer cells. We successfully developed a highly selective room-temperature phosphorescent probe to detect the human cancer cells with the overexpressed NQO1
(2) Highly selective and sensitive colorimetric detection of Ag(I) using N-1-(2-mercaptoethyl)adenine functionalized gold nanoparticles
A sensitive and selective colorimetric Ag+ detection method was developed by using N-1-(2-mercaptoethyl)adenine functionalized gold nanoparticles (MEA-AuNPs). The presence of Ag+ immediately induced aggregation of MEA-AuNPs, yielding a color change from wine-red to purple. This Ag+-induced aggregation of MEA-AuNPs was monitored by bare eye and UV-vis spectroscopy with a detection limit of 3.3 nM. MEA-AuNPs showed excellent selectivity toward Ag+ compared with other metal ions through interaction between adenine and Ag+. The best detection of Ag+ was achieved at pH 6-9. Furthermore, MEA-AuNPs were applied to detect Ag+ in lake water with low interference.
(3) Colorimetric detection of Cd(II) ions based on di(1H-pyrrol-2-yl)methanethione functionalized gold nanoparticles
A sensitive and selective colorimetric Cd2+ detection method was developed using di(1H-pyrrol-2-yl)methanethione functionalized gold nanoparticles (DP-AuNPs). Aggregation of DP-AuNPs was induced immediately in the presence of Cd2+, yielding a color change from wine-red to purple. This Cd2+-induced aggregation of DP-AuNPs was monitored using the naked eye and UV-Vis spectroscopy with a detection limit of 16.6 nM. The DP-AuNPs showed excellent selectivity toward Cd2+ compared to other metal ions through the interaction between di(1H-pyrrol-2-yl)methanethione and Cd2+. Optimal detection of Cd2+ was achieved over a pH range from 4 to 9.5. Furthermore, DP-AuNPs were applied to detect Cd2+ in lake water, showing low interference.
URI: http://140.113.39.130/cdrfb3/record/nctu/#GT079825805
http://hdl.handle.net/11536/74275
显示于类别:Thesis