二卤代荧光素衍生物的荧光性能调控.pdf

第30卷第7期
无机化学学报
Vol 30 No. 7
2014年7月
CHINESE JOURNAL OF INORGANIC CHEMISTRY
1582-1586
二鹵代荧光素衍生物的荧光性能调控
刘丽敏2张先付*,3
(河北科技师范学院应用光化学研究所,秦皇岛066004)
(安徽理エ大学化工学院,准南232001)
(MPC Technologies, Hamilton, Ontario, Canada L8S 3H4)
摘要:用紫外可见吸收光谱、稳态/瞬态荧光光谱和单线态氧捕捉等方法分别测量了荧光素钠及4,5位-二卤代荧光素钠(FLX,
X=H,CL,Br,的电子吸收光谱、荧光光谱、荧光量子效率()、荧光寿命()和单线态氧量子产率(の),并与荧光素钠的相应性质
进行了比较。对应于X=H,Cl,Br,,HLX2的值分别为0.92、096、0.690.16;r值分别为4.16、,4.72、3.50,0.80ms;Φ。值分别为
0.0034、0.049、0.30、0.68。随着氯、溴、碘原子量增大,相应的の4和r值并非顺序减小,5っ值逐渐增大,只用重原子效应不能解
释二卤代荧光素的荧光和光敏性质变化,而结合分子内光诱导电子转移就能较好的解释实验结果。
关键词:荧光素;荧光;单线态氧;重原子效应;光诱导电子转移
中图分类号:0644
文献标识码:A文章编号:1001-4861(2014)07-1582-05
DOI:10.11862/CJIC.2014.244
Fluorescence Performance Tuning for Dihalogenated Fluorescein Derivatives
L U Ii-minl2 ZHANG Xian-fu*13
Institute of Applied ot hemistry, Hebei Normal Unie sity of Science Technology, huangdao, Hebei 066004, China)
(School ofchemical Engineering, A nhui University o Science echnology, Huainan, Anhui 232001, China)
( MPC Technologies, Hamilton, Ontario, Canada L8S 3H4
Abstract: The fluorescence quantum yield (), fluorescence lifetime( and singlet oxygen formation quantum
ield (C)of fluorescein and 4, 5-d halogenated fluoresceins in their dianion forms(FLX,, X=H, C, Br, I)were
characterized by using Uv-vis spectroscopy, steady-state/time-resolved fluorescence and singlet oxygen traping
technique. The @e value is 0.92, 0.96, 0.69, and 0.16; the Tr value is 4.16, 4.72, 3.50 and 0.80 ns; the a value
is 0.003 4, 0.049, 0.30, and 0.68 for FLX2 (X=H, Cl, Br, I), respectively. In comparison with that of fluorescein,
the increase of atom size from Cl, Br to I does not cause the decrease of r and Tr monotonically, so that heavy
atom effect alone cannot explain the experimental results. The observations can be rationalized by the presence of
intramolecular photo-induced electron transfer, in which the benzonate acts as the electron donor while the
xanthene moiety is the acceptor.
Keywords: fluorescein; fluorescence; singlet oxygen; heavy atom effect; photoinduced electron transfer
荧光素及其衍生物的分子结构(图1)由相对独光量子产率、好的生物相容性以及独特的光谱性
立的两部分(即上半部分的苯环和下半部分的占吨质,荧光素及其衍生物广泛应用于DNA排序叫、激
环)构成,这两部分几乎垂直而不共轭。由于其高荧光染料、追踪试剂門、单线态氧光敏剂间、荧光检
收稿日期;2013-12-01。收修改稿日期:2014-04-11
河北省自然科学基金(N-B2014407080)资助项目。
通讯联系人。E-mil:zhangxianfu(@tsinghua.org.cn