银纳米立方体对诺丹明分子的荧光增强或猝灭效应实验研究

摘要/Abstract

摘要：

用乙二醇还原硝酸银，成功制备了平均边长约97 nm的银纳米立方体以用于诺丹明(RhB)分子的荧光实验。实验中，将探针分子 RhB 粉末掺杂于PMMA苯甲醚溶液中，制得不同厚度参杂有RhB探针分子的PMMA薄膜，运用光谱技术和共焦显微技术研究了银纳米立方体与荧光分子的间隔、银纳米立方体不同浓度分布对RhB分子的荧光强度的影响。荧光光谱表明，荧光强度随PMMA厚度变薄而增强，当PMMA厚度为10nm时，荧光增强因子最大，获得了56倍的荧光增强效果，而继续减小PMMA厚度时，其荧光增强因子又变小，说明发生了荧光猝灭效应。共焦荧光像则更直观地表现了银纳米立方体的浓度分布对荧光分子辐射增强的影响。因而，可通过调控银纳米立方体与荧光分子的距离及银纳米立方体的分布优化荧光增强因子以用于基于荧光的单分子探测，这一实验结果在生物成像和生物传感领域有潜在应用价值。

关键词: 光谱学, 增强荧光, 表面等离子体激元, 局域场增强, 银纳米立方体

Abstract:

Silver nano-cubes of about 97nm side-length were synthesized by reducing AgNO3 with ethylene glycol (EG) and used to modulate fluorescence intensity of Rhodamine B (RhB). The RhB (probe molecules) powder were dissolved into PMMA solution with different PMMA concentrations, which were resulted in RhB doped PMMA films of different thickness. The distance between Ag nano-cubes and the fluorescence molecules and the distribution of Ag nano-cubes have important influence on the fluorescence emission. The fluorescence spectrums show the enhancement and quenching effect with different thickness of PMMA film. The largest fluorescence enhancement factor (EF) is 56 for the structure of Ag nano-cubes absorbed on the RhB doped PMMA film as the thickness of PMMA is 10nm. The confocal-images also verified the fluorescence enhancement. The EF is influenced by the distribution of silver nano-cubes on the PMMA film from the confocal-images. So the biggest EF can be obtained by optimizing the distance between silver nano-cubes and the fluorescence molecules or by tuning the distribution of silver nano-cubes, which may be used to single molecule detection. The experiment results have potential application in fluorescence based bio-sensing or bio-imaging.

Key words: spectroscopy, enhanced fluorescence, surface plasmon polaritons, localized field enhancement, silver nano-cubes

中图分类号:

O482.31

易明芳张杰赵玉杰马业万朱德权祝祖送尤建村夏强胜. 银纳米立方体对诺丹明分子的荧光增强或猝灭效应实验研究[J]. J4, 2013, 30(5): 513-519.

Yi Mingfang, Zhang Jie, Zhao Yujie , Ma Yewan, Zhu Dequan, Zhu Zusong, You Jiancun, Xia Qiangsheng . Experimental investigation of fluorescence enhancement or quenching of Rhodamine B molecules caused by silver nano-cubes[J]. J4, 2013, 30(5): 513-519.

参考文献

[1] Fu Y, Lakowicz JR. Modification of single molecule fluorescence near metallic nanostructures[J]. Laser & Photon Rev , 2009, 3(1-2):12.
[2] Zhang J, Fu Y, Chowdhury MH, Lakowicz JR. Metal-Enhanced Single-Molecule Fluorescence on Silver Particle Monomer and Dimer: Coupling Effect between Metal Particles[J]. 2007, Nano Lett, 7(7):7.
[3] Cade NI, Ritman-Meer T, Kwakwa KA, Richards D.The plasmonic engineering of metal nanoparticles for enhanced fluorescence and Raman scattering[J]. Nanotechnology, 2009, 20(285201):7.
[4] Hung Y-J, Smolyaninov II, Davis CC. Fluorescence enhancement by surface gratings[J]. OPTICS EXPRESS, 2006, 14(22):6.
[5] Hwang E, Smolyaninov II, Davis CC. Surface Plasmon Polariton Enhanced Fluorescence from Quantum Dots on Nanostructured Metal Surfaces[J]. Nano Lett, 2010, 10:8.
[6] Lakowicz JR, Shen Y, D'Auria S, Malicka J, Fang J, Gryczynski Z, Gryczynski I.Radiative Decay Engineering 2. Effects of Silver Island Films on Fluorescence Intensity, Lifetimes, and Resonance Energy Transfer[J]. Anal Biochem, 2002,301:17.
[7] Geddes CD, Lakowicz JR. Metal-Enhanced Fluorescence[J]. J Fluoresc, 2002,12(2):9.
[8] Kinkhabwala A, Yu Z, Fan S, Avlasevich Y, KlausMu¨llen, Moerner WE.Large single-molecule fluorescence enhancements produced by a bowtie nanoantenna[J]. NATURE PHOTONICS , 2009, 3(11):4.
[9] Dou-Guo Z, Pei W, Xiao-Jin J, Xiao-Hong S, Guang-Hui Y, Jiang-Ying Z, Yan D, Hai M, You-Yi S, Jing-Li Z et al.Fluorescence Enhancement of a Polymer Planar Waveguide Doped with Rhodamine B and Ag Nanoparticles[J]. Chinese Phys Lett, 2006, 23(10):5.
[10] Hutter E, Janos.H.Fender. Exploitation of Localized Surface plasmon resonance[J]. AdvMater, 2004, 16(19):22.
[11] Zayats AV, Smolyaninov II. Near-field photonics: surface plasmon polaritons and localized surface plasmons[J]. J Opt A: Pure Appl Opt , 2003, 5:36.
[12] Anger P, Bharadwaj P, Novotny L. Enhancement and Quenching of Single-Molecule Fluorescence[J]. PRL , 2006, 96(113002 ):4.
[13] CY L, KC C, CY C, SH C, TF G, SJ. C.Surface plasmon-enhanced and quenched two-photon excited fluorescence[J]. Opt Express, 2010, 18(12):17.
[14] Castanié E, Boffety M, Carminati R.Fluorescence quenching by a metal nanoparticle in the extreme near-field regime[J]. Opt Lett, 2010,35(3):4.
[15] Skrabalak SE, Au L, Li X, Xia Y. Facile synthesis of Ag nanocubes and Au nanocages[J]. NATURE PROTOCOLS, 2007, 2(9):9.
[16] Zhang DG, Yuan X-C, Bouhelier A, Wang P, Ming H. Excitation of surface plasmon polaritons guided mode by Rhodamine B molecules doped in a PMMA stripe[J]. Opt Lett, 2010, 35(3):3.
[17] Zhang YX, Dragan A, Geddes CD.Broad Wavelength Range Metal-Enhanced Fluorescence Using Nickel Nanodeposits[J]. J Phys Chem C, 2009, 113(36):6.
[18] Zhang D, Yuan X, Bouhelier A. Direct image of surface-plasmon-coupled emission by leakage radiation microscopy[J]. Appl Optics, 2010,49(5):5.
[19] Zhang DG, Moh KJ, Yuan X-C.Surface plasmon-coupled emission from shaped PMMA films doped with fluorescence molecules[J]. Opt Express, 2010,18(12):6.
[20] Valeur B:2001 Molecular Fluorescence: Principles and Applications[M]. In.: Wile y-VCH Verlag GmbH.
[21] Lakowicz JR.Radiative decay engineering 5: metal-enhanced fluorescence and plasmon emission[J]. Anal Biochem, 2005, 337:24.
[22] Mattei G, Mazzoldi P, Bernas H. Metal Nanoclusters for Optical Properties[J]. In.: Berlin: Springer.
[23] Maier SA: 2007 PLASMONICS:FUNDAMENTALS AND APPLICATIONS[J]. 1995, 234.
[24] Kravets VG, Zoriniants G, Burrows CP, Schedin F, Casiraghi C, Klar P, Geim AK, Barnes WL, Grigorenko AN.Cascaded Optical Field Enhancement in Composite Plasmonic Nanostructures[J]. PRL, 2010, 105(246806):4.
[25] Grigorenko AN, Kravets VG, Zoriniants G, Burrows CP, Schedin F, Geim AK, Barnes WL.Composite Au Nanostructures for Fluorescence Studies in Visible Light[J]. Nano Lett, 2010,10(3):874-879.
[26] Kim K, Lee YM, Lee JW, Shin KS.Metal-Enhanced Fluorescence of Rhodamine B Isothiocyanate from Micrometer-Sized Silver Powders[J]. Langmuir, 2009, 25:6.
[27] Farc?u C, A?tilean S.Silver half-shell arrays with controlled plasmonic response for fluorescence enhancement optimization[J]. Appl Phys Lett. :2009, (95):3.
[28] Mackowski S, Wormke S, Maier AJ, Brotosudarmo THP, Harutyunyan H, Hartschuh A, Govorov AO, Scheer H, Brauchle C. Metal-enhanced fluorescence of chlorophylls in single light-harvesting complexes[J]. Nano Lett, 2008, 8(2):558-564.
[29] Aslan K, Leonenko Z, Lakowicz JR, Geddes CD. Fast and Slow Deposition of Silver Nanorods on Planar Surfaces: Application to Metal-Enhanced Fluorescence[J]. J Phys Chem B, 2005.109:6.
[30] M.Bakker R, Yuan H-K, Liu Z, Drachev VP, Kildishev AV, Shalaev VM. Enhanced localized fluorescence in plasmonic nanoantennae[J]. Appl Phys Lett. 2008, (92):3.
[31] Parfenov A, Gryczynski I, Malicka J, Geddes CD, Lakowicz JR. Enhanced Fluorescence from Fluorophores on Fractal Silver Surfaces[J]. J Phys Chem B. 2003, (107):5.
[32] Thomas PonsIgor L. Medintz, Kim E. Sapsford, et al. On the quenching of semiconductor quantum dot photoluminescence by proximal gold nanoparticles[J]. Nano Lett, 2007,7(10):8.