Study on Synthesis of Amino-phenanthroline-Ru (Ⅱ) Phosphor and Its Chemical Immobilization onto PMMA

doi:10.7517/j.issn.1674-0475.2015.06.513

Abstract

Abstract:

To alleviate phosphor leaching and prolong the lifetime of fluoresce quenching sensors, a reactive phosphor [Ru(dpp)₂(phen-NH₂)]Cl₂ was synthesized through the ligation between [Ru(dpp)₂(phen-NH₂)]Cl₂ and 5-amino-phenanthroline (phen-NH₂) and immobilized to PMMA surface through covalent bonding. The structure of the synthesized phosphor and covalent bonding were verified with FT-IR, ¹HNMR, ¹³CNMR spectroscopy, UV-Vis and ES-MS. The effects of reaction conditions on the fluorescence of PMMA immobilized with phosphors were investigated and the fluorescent decay of the PMMA in 50 ℃ water was monitored. The fluorescent emission of the synthesized [Ru(dpp)₂(phen-NH₂)]Cl₂ in ethanol peaked at 570 nm and red shifted 20 nm as chemically bonded to PMMA. [Ru(dpp)₂(phen-NH₂)]Cl₂ bonded to PMMA exhibited fast response speed to dissolved oxygen and the oxygen quenching ratio I₀/I₁₀₀ was 4. After immersed in water at 50 ℃ for more than 90 days, the fluorescence intensity of PMMA bonded with [Ru(dpp)₂(phen-NH₂)]Cl₂ decreased less than 1%.

Key words: Ru(Ⅱ) phosphors, reactive phosphors, chemical bonding, oxygen sensitive fluorescent membrane, reliability

HU Xiaoying, LI Jianxiong, LIU Anhua. Study on Synthesis of Amino-phenanthroline-Ru (Ⅱ) Phosphor and Its Chemical Immobilization onto PMMA[J]. Imaging Science and Photochemistry, 2015, 33(6): 513-520.

References

[1] 姜德生,陈兴,黄俊.用热聚法固定指示剂的光纤氧气传感器研究[J].化学学报,2003,61(8):1281-1286. Jiang D S, Chen X, Huang J.Study on new fiber optic oxygen sensor with immobilizing the indicator by thermo-polymerization Method[J]. Acta Chimica Sinica, 2003, 61(8): 1281-1286.
[2] 胡静,吕凤婷,房喻.光学薄膜氧气传感器研究进展[J].化学研究与应用,2007,19(5):458-461. Hu J, Lv F T, Fang Y. Progress in the studies of optical oxygen film sensors[J].Chemical Research and Application, 2007,19(5):458-461.
[3] Brian D M, Colette M M, Gerard O.Fiber optic oxygen sensor based on fluorescence quenching of evanescent-wave excited ruthenium complexes in sol gel derived porous coatings[J].Analyst,1993,118(4): 385-388.
[4] Bacon J R, Demas J N. Determination of oxygen concentrations by luminescence quenching of a polymer-immobilized transition-metal complex[J]. Analytical Chemistry, 1987, 59(23): 2780-2785.
[5] Carraway E R, Demas J N, DeGraff B A, Bacon J R. Luminescence quenching mechanism for microheterogeneous systems[J]. Analytical Chemistry,1991,63(4): 332-336.
[6] 吕太平, Stefan R, Ursular E S.基于新的亲脂性荧光试剂的光纤O₂传感器的研制[J].化学传感器,1997, 17(4):279-281. Lv T P, Stefan R, Ursular E S. Development of optical fiber O₂ sensor based on new lipophilic fluorescence compounds[J].Chemical Sensors,1997,17(4):279-281.
[7] Wu X D, Song L T, Li B, Liu Y H. Synthesis, characterization, and oxygen sensing properties of Ru(Ⅱ) complex covalently grafted to mesoporous MCM-41[J].Journal of Luminescence,2010,130(3):374-379.
[8] 苗雨. 基于卟啉基团的聚合物溶解氧传感器的合成及性能研究[D]. 上海: 华东理工大学, 2012. Miao Y. Synthesis and properties of polymeric dissolved oxygen sensor based on porphyrin unit[D]. Shanghai: East China University of Science and Technology, 2012.
[9] Jin P W,Guo Z Q, Zhu J,Tan J, Zhang S L, Zhu W H.Screen-printed red luminescent copolymer film containing cyclometalated iridium(Ⅲ) complex as a high-permeability dissolved-oxygen sensor for fermentation bioprocess[J].Industrial and Engineering Chemistry Research, 2013,52(11):3980-3987.
[10] 李建雄,左陈,陈建明,李炳蔚.改性SiO₂载体对邻菲咯啉钌荧光特性及氧敏感荧光膜性能的影响[J].影像科学与光化学, 2015,33(3):211-217. Li J X, Zuo C, Chen J M, Li B W. Effect of phosphor carriers on fluorescence of ruthenium phenanthroline and performance of oxygen-sensitive fluorescent membranes[J].Imaging Science and Photochemistry, 2015,33(3):211-217.
[11] Nikolay K, Mihail N, Diana W W, Georgi D D. Synthesis and biological activity of novel heavy metal complexes of 5-amino-1,10-phenanthroline and 1,10-phenanthroline[J].Central European Journal of Chemistry, 2012,10(4): 1034-1041.
[12] Hyung J K,Yong C J, Taek H K. Synthesis of tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(Ⅱ) complexes possessing a linker arm for use in Sol-gel-based optical oxygen sensor[J]. Bulletin of the Korean Chemical Society, 2006, 27(12):2084-2086.
[13] Song C H, Ye Z Q, Wang G L, Jin D Y, Yuan J L, Guan Y F, James P. Preparation and time-gated luminescence bioimaging application of ruthenium complex covalently bound silica nanoparticles[J].Talanta,2009,79(1): 103-108.
[14] 苑嗣纯,陈海波,王惠川.联三吡啶配体组装及其金属配合物性能[J].化学进展,2009,21(10):2132-2152. Yuan S C, Chen H B, Wang H C. Assembly and metal complex properties of terpyridine ligands[J].Progress in Chemistry, 2009,21(10):2132-2152.
[15] 施建军,吕卫星,王怀兵,高建峰.菲咯啉类有机钌络合物的合成及其光谱分析[J].应用化学, 1998,15(6):68-70. Shi J J, Lv W X, Wang H B, Gao J F. Synthesis and spectral analysis of ruthenium complexes with phenathroline derivatives[J].Chinese Journal of Applied Chemistry, 1998,15(6):68-70.
[16] 周冬秋,肖韶荣,肖林.基于荧光猝灭原理的光纤溶解氧传感器研制[J].光学与光电技术, 2013,11(4):64-66. Zhou D Q, Xiao S R, Xiao L. Development of fiber optic dissolved oxygen sensor based on fluorescence quenching[J]. Optic & Optoelectronic Technology, 2013,11(4):64-66.
[17] 冯长根,白林山,任启生.胺基化合物修饰戊二醛交联壳聚糖树脂的合成及其红外光谱研究[J].光谱学与光谱分析, 2004,24(11):1315-1318. Feng C G, Bai L S, Ren Q S. Preparation and FTIR properties of amino compounds modified glutaraldehyde crosslinked chitosan resin activated with cyanuric chloride[J]. Spectroscopy and Spectral Analysis, 2004,24(11):1315-1318.
[18] 赵一兵,王冬媛,许可慰,郭祥群,许金钩.一类自猝灭的新型荧光探针研究[J].厦门大学学报,1997,36(4):594-598. Zhao Y B, Wang D Y, Xu K W, Guo X Q, Xu J G. Study on a self-quenching fluorescence probe[J].Journal of Xiamen University(Natural Science), 1997,36(4):594-598.