Lanthanide magneto-luminescent and plasmonic (Gd2O3:Eu@AuNR) nanoassembly for the turn-on fluorescence detection of nitro aromatic compound

  • G. L. Praveen
  • G. M. Lekha
  • V. M. Visakh
  • L. R. Reshma
  • Sony George
Research Paper


In this study, we design a nanoassembly-based chemosensor possessing the fluorescence in the visible region which comes into play for analyte detection in aqueous medium. Here, Mercaptopropionic acid-functionalised nanophosphor (Gd2O3:Eu @ MPA) acts as donor, and the Cysteamine functionalised gold nanorod (AuNR @ Cysteamine) acts as the acceptor molecule. The working principle of this nanoassembly is the FRET phenomenon which happens between nanophosphors and gold nanorods through amine-carboxyl attractive interactions (Turn-Off) followed by the Meisenheimer complex formation between –NO2 groups of TNT and primary amines of the Cysteamine functionalised AuNR (Turn-On) which gives corresponding fluorescent signals in the visible regions. The fluorescence turn-on is immediate, and the limit of detection is as low as 11.88 x 10−9 M. The above-mentioned phenomena were substantiated using the UV–Visible, Photoluminescence, and Time-Correlated Single Photon Counting spectroscopic techniques. The size, morphology, particle interactions, charge, and functionalisations were substantiated through TEM, DLS, Zeta potential, and FTIR techniques. The size variations happened to the AuNR in three different stages are evident from the TEM images. (i) when AuNR (Gold nanorod) is present alone, i.e. LnNp and TNT free system, the average size of AuNR was 15.17 nm (ii) When LnNp (Lanthanide Nanophosphor) was added (attached), i.e. AuNR + LnNp involved state, the average size of AuNR was increased to 23.05 nm (iii) When TNT was introduced to AuNR + LnNp system (Analyte attachment and LnNp detachment happening state) i.e. AuNR + LnNp + TNT involved state, the average size of AuNR was decreased to16.3 nm as it was in its pristine form. The same trend was obtained for the DLS measurements.


Lanthanide Nanophosphor Gold nanorod Magneto-Luminescent FRET Turn-on sensor Photonics 



The authors thank the Head of CSIR-NIIST (Pappanamcode), CESS (Thiruvananthapuram), SAIF-IIT (Madras), SCT-IMST (Poojapura), Departments of Bio-Technology & Bio-Chemistry, University of Kerala, Kariavattom campus, (Thiruvananthapuram) for the sophisticated characterization techniques provided for the work.

Supplementary material

11051_2014_2522_MOESM1_ESM.pptx (529 kb)
Fig. S1. The VSM plot of Gd2O3: Eu@MPA Lanthanide nanophosphor taken at Room Temperature. Fig. S2 The Zeta potential (ξ) distribution curve of Gd2O3: Eu@MPA Lanthanide nanophosphor Fig. S3 The Zeta potential (ξ) distribution curve of AuNR@Cysteamine. Fig. S4 FT-IR spectrum of MPA modified LnNP (Gd2O3: Eu@MPA) Fig. S5 FT-IR spectrum of Cysteamine modified AuNR-626 Fig. S6 The DLS size distribution of individual AuNR @ cystemine system Fig. S7 The DLS size distribution of LnNP @MPA: AuNR @ cystemine system Fig. S8 The DLS size distribution of LnNP @MPA: AuNR @ cystemine + TNT system (PPTX 529 kb)
11051_2014_2522_MOESM2_ESM.doc (39 kb)
Supplementary material 2 (DOC 39 kb)


  1. Aditya Narayanan, Varnavski OP, Swager TM, Theodore Goodson (2008) Multiphoton fluorescence quenching of conjugated polymers for TNT Detection. J Phys Chem C 112:881–884CrossRefGoogle Scholar
  2. Chandra S, Doran J, McCormack SJ, Kennedy M, Chatten AJ (2012) Enhanced quantum dot emission for luminescent solar concentrators using plasmonic interaction. Sol Energy Mater Sol Cells 98:385–390CrossRefGoogle Scholar
  3. Changmin Deng, Pei Gong, Qingguo He, Jiangong Cheng, Chao He, Liqi Shi, Defeng Zhu, Tong Lin (2009) Highly Fluorescent TPA-PBPV nanofibers with amplified sensing response to TNT. Chem Phys Lett 483:219–223Google Scholar
  4. Colton RJ, Russell JN (2003) Making the world a safer place. Science 299:1324–1325CrossRefGoogle Scholar
  5. Daming Gao, Zhenyang Wang, Bianhua Liu, Lin Ni, Minghong Wu, Zhongping Zhang (2008) Resonance Energy Transfer-Amplifying Fluorescence Quenching at the surface of silica Nanoparticles towards ultra sensitive detection of TNT. Anal Chem 80:8545–8553CrossRefGoogle Scholar
  6. Doose S, Neuweiler H, Sauer M (2005) A close look at fuorescence quenching of organic dyes by tryptophan. Chem Phys Chem 6:2277–2285Google Scholar
  7. Dosev D, Kennedy IM, Godlewski M, Gryczynski I, Tomsia K, Goldys EM (2006) Fluorescence upconversion in Sm-doped Gd2O3. Appl Phys Lett 88:11906–11909CrossRefGoogle Scholar
  8. Ferrer E, de Leon M, Hernandez-Rivera SP (2005) Nanoscaled science and engineering for trace explosive sensing: The effect of TNT concentration in the fluorescence emission of CdS quantum dots. Abstracts of papers of the American Chemical Society-230: U267-U267.Google Scholar
  9. Gai S, Yang P, Wang D, Li C, Niu Na, Hea F, Lia X (2011) Monodisperse Gd2O3:Ln (Ln = Eu3 + , Tb3 + , Dy3 + , Sm3 + , Yb3 +/Er3 + , Yb3 +/Tm3 + , and Yb3 +/Ho3 +) nanocrystals with tunable size and multicolor luminescent properties. Cryst Eng Comm 13:5480–5487CrossRefGoogle Scholar
  10. Gao F, Cui P, Chen X, Ye Q, Li M, Wang L (2011) An efficient phosphorescence energy transfer between quantum dots and carbon nanotubes for ultrasensitive turn-on detection of DNA. Analyst 136:3973–3980CrossRefGoogle Scholar
  11. Germain ME, Knapp MJ (2009) Optical explosives detection: from color changes to fluorescence turn-on. Chem Soc Rev 38:2543–2555CrossRefGoogle Scholar
  12. Haixia Zhang, Lijuan Feng, Bingxin Lin, Cuiyan Tong, Changli Lu (2014) Conjugation of PPV functionalized mesoporous silica nanoparticles with graphene oxide for facile and sensitive fluorescence detection of TNT in water through FRET. Dyes Pigm 101:122–129CrossRefGoogle Scholar
  13. Hallowell SF (2001) Raman and Infrared Microspectroscopy of the High Explosives TNT, PETN, and RDX heated to their Melting Point and Beyond. Talanta 54:447–458CrossRefGoogle Scholar
  14. Hodak JH, Henglein A, Hartland GV (2000) Electron-phonon coupling dynamics in very small between 2 and 8 nm diameter Au nanoparticles. J Chem Phys 112:5942–5947Google Scholar
  15. Jehuda Y, Johonson VJ, Bernier R, Yost U, Mayfield AR, Mahone TH, Vorbeck WC (2005) Reactions in the mass spectrometry of a hydride meisenheimer complex of 2,4,6-trinitrotoluene (TNT). J Mass Spectrom 30:715–722Google Scholar
  16. Kolla P (1997) The Application of Analytical Methods to the Detection of Hidden Explosives and Explosive Devices. Angew Chem 36:800–811CrossRefGoogle Scholar
  17. Kulakovich O, Strekal N, Yaroshevich A, Maskevich S (2002) Enhanced Luminescence of CdSe Quantum Dots on Gold Colloids. Nano Lett 2:1449–1452CrossRefGoogle Scholar
  18. Lakowicz JR (2006) Principles of Fluorescence Spectroscopy. Springer-Verlag, Berlin HeidelbergCrossRefGoogle Scholar
  19. Lijuan Feng, Chungn Wang, Zhonglin Ma, Changli Lu (2013) 8-Hydroxyquinoline functionalized ZnS nanoparticles capped with amine groups: a fluorescent nanosensor for the facile and sensitive detection of TNT through fluorescence resonance energy transfer. Dyes Pigm 97:84–91CrossRefGoogle Scholar
  20. Link S, El-Sayed MA (1999) Spectral Properties and Relaxation Dynamics of Surface Plasmon Electronic Oscillations in Gold and Silver Nanodots and Nanorods. J Phys Chem B 103:8410–8426Google Scholar
  21. Moore DS (2004) Instrumentation for trace detection of high explosives. Rev Sci Instrum 75:2499–2512CrossRefGoogle Scholar
  22. Murphy CJ, Thompson LB, Alkilany AM, Sisco PN, Boulos SP, Sivapalan ST, Yang JA, Chernak DJ, Huang J (2010) The Many Faces of Gold Nanorods. J Phys Chem Lett 1:2867–2875Google Scholar
  23. Nikobakht B, El-Sayed MA (2003) Preparation and Growth Mechanism of Gold Nanorods (NRs) Using Seed-Mediated Growth Method. Chem Mater 15:1957–1962CrossRefGoogle Scholar
  24. Pandya Alok, Goswami Heena, Lodha Anand, Menon Shobhana K (2012) A novel nanoaggregation detection technique of TNT using selective and ultrasensitive nanocurcumin as a probe. Analyst 137:1771–1774CrossRefGoogle Scholar
  25. Qian JJ, Qiu LG, Wang YM, Yuan YP, Xie AJ, Shen YH (2014) Fabrication of magnetically separable fluorescent terbium-based MOF nanoparticles for highly selective trace level detection of TNT. Dalton Trans 43:3978–3983CrossRefGoogle Scholar
  26. Renyong Tu, Bianhua Lin, Zhenyag Wang, Daming Geo, Fens Wang, Qunling Fang, Zhongping Zhang (2008) Amine capped ZnS-Mn2+ Nanocrystals for Fluorescence Detection of Trace TNT explosive. Anal Chem 80:3458–3465CrossRefGoogle Scholar
  27. Rodenas A, Zhou G, Jaque D, Gu M (2009) Photonic Properties of Inverse Opals Fabricated from Lanthanide-Doped LaPO4 Nanocrystals. Adv Mater 21:3883–3888CrossRefGoogle Scholar
  28. Sapsford KE, Berti L, Medintz IL (2006) Materials for fluorescence resonance energy transfer analysis: beyond traditional donor-acceptor combinations. Angew Chem 45:4562–4588CrossRefGoogle Scholar
  29. Shengyang Tao, Guangtao Li, Jinxiang Yin (2007) Fluorescent nanofibrous membranes for trace detection of TNT vapour. J Mater Chem 17:2730–2736Google Scholar
  30. Singh S, Hazard J (2007) Sensor an effective approach for the detection of explosives. Mater 144:15–28Google Scholar
  31. Steinfeld JI, Wormhoudt J (1998) Explosives detection: a challenge for physical chemistry. Annu Rev Phys Chem 49:203–232Google Scholar
  32. Sun J, Ge J, Liu W, Fan Z, Zhang H, Wang P (2011) Highly sensitive and selective colorimetric visualization of streptomycin in raw milk using Au nanoparticles supramolecular assembly. Chem Commun 47:9888–9890CrossRefGoogle Scholar
  33. Swager TM, Esser B (2010) Detection of Ethylene gas by fluorescence Turn-on of a conjugated polymer. Angew Chem 122:9056–9059CrossRefGoogle Scholar
  34. Tanner PA, Fu LS, Cheng BM (2009) Spectral Band Shifts in the Electronic Spectra of Rare Earth Sesquioxide Nanomaterials Doped with Europium. J Phys Chem C 113:10773–10779CrossRefGoogle Scholar
  35. Thomas KG, Kamat PV (2003) Chromophore-functionalized gold nanoparticles. Acc Chem Res 36:888–898CrossRefGoogle Scholar
  36. Tong L, Liu D, Shi Jianhui, Yang Xuwei, Yang Hua (2012) Magnetic and Luminescent properties of Fe3O4 @Y2O3:Eu3+ nanocomposites. J Mater Sci 47:132–137CrossRefGoogle Scholar
  37. Walker NR, Linman MJ, Timmers MM, Dean SL, Burkett CM, Lloyd JA, Keelor JD, Baughman BM, Edmiston PL (2007) Selective detection of gas-phase TNT by integrated optical waveguide spectrometry using molecularly imprinted sol-gel sensing films. Anal Chim Acta 593:82–91CrossRefGoogle Scholar
  38. Wang C, Irudayaraj J (2010) Multifunctional Magnetic-Optical Nanoparticle Probes for Simultaneous Detection, Separation, and Thermal Ablation of Multiple Pathogens. Small 6:283–289CrossRefGoogle Scholar
  39. Wang Ya-qin, Zou Wen-Sheng (2011) 3-Aminopropyl triethoxysilane functionalized manganese doped ZnS quantum dots for room-temperature phosphorescence sensing ultra trace 2,4,6- trinitrotoluene in aqueous solution. Talanta 85:469–475CrossRefGoogle Scholar
  40. Woodfin RL (2007) Trace Chemical Sensing of Explosives. John Wiley & Sons, HobokenGoogle Scholar
  41. Xia Y, Song L, Zhu C (2011) Turn-On and Near-Infrared Fluorescent Sensing for 2,4,6-Trinitrotoluene Based on Hybrid (Gold Nanorod) − (Quantum Dots) Assembly. Anal Chem 83:1401–1407Google Scholar
  42. Yinon Y (2007) Counterterrorist Detection Techniques of Explosives. Elsevier, AmsterdamGoogle Scholar
  43. Zhou Dan-Ling, Huang Hong, Zheng Jie-Ning, Chen Jian-Rong, Feng Jiu-Ju, Wang Ai-Jun (2013) Polyinosinic acid-stabilized fluorescent silver nanoclusters for sensitive detection of biological thiols. Anal Methods 5:6076–6080CrossRefGoogle Scholar
  44. Zou Wen-Sheng, Sheng Dong, Ge Xin, Qiao Jun-Qin, Lian Hong-Zhen (2011a) Room-Temperature Phosphorescence Chemosensor and Rayleigh Scattering Chemodosimeter Dual-Recognition Probe for 2,4,6-Trinitrotoluene Based on Manganese-Doped ZnS Quantum Dots. Anal Chem 83:30–37CrossRefGoogle Scholar
  45. Zou Wen-Sheng, Qiao Jun-Qin, Xin Hu, Ge Xin, Lian Hong-Zhen (2011b) Synthesis in aqueous solution and characterisation of a new cobalt-doped ZnS quantum dot as a hybrid ratiometric chemosensor. Anal Chim Acta 708:134–140CrossRefGoogle Scholar
  46. Zou Wen-Sheng, Yang Jin, Yang Ting–Ting, Xin Hu, Lian Hong-Zhen (2012) Magnetic-Room temperature phosphorescent multifunctional nanocomposites as chemosensor for detection and photo-driven enzyme mimetics for degradation of 2,4,6-trinitrotoluene. J Mater Chem 22:4720–4727Google Scholar
  47. Zou Wen-Sheng, Wang Ya-qin, Wang Feng, shao Qun, Zhang Jun, Liu Jin (2013) Selective Fluorescence response and magnetic separation probe for 2,4,6- trinitrotoluene based on iron oxide magnetic nanoparticles. Anal Bioanal Chem 405:4905–4912CrossRefGoogle Scholar
  48. Zou Wen-Sheng, Zou Fei-Hua, Shao Qun, Zhang Jun, Wang Ya-qin, Xie Fa-Zhi, Ding Yi (2014) A selective fluorescence resonance energy transfer quenching and resonance light scattering enchancement dual-recognition probe for 2,4,6- trinitrotoluene. J. Photochem. Photobio. A 278:82–88CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2014

Authors and Affiliations

  • G. L. Praveen
    • 1
  • G. M. Lekha
    • 1
  • V. M. Visakh
    • 1
  • L. R. Reshma
    • 1
  • Sony George
    • 1
  1. 1.Department of ChemistryUniversity of KeralaTrivandrumIndia

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