4.6 Article

Electrochemiluminescence Detection of TNT by Resonance Energy Transfer through the Formation of a TNT-Amine Complex

Journal

CHEMISTRY-A EUROPEAN JOURNAL
Volume 20, Issue 16, Pages 4829-4835

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201303710

Keywords

analytical methods; charge transfer; electrochemiluminescence; explosives; resonance-energy transfer

Funding

  1. National Natural Science Foundation of China [21175126]
  2. Faculty Development Program of Bahauddin Zakaryia University, Multan, Pakistan [PF/Cont./2-50/Admin/5398]
  3. Academy of Sciences for the Developing World (TWAS)
  4. Chinese Academy of Sciences (CAS)

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2,4,6-Trinitrotoluene (TNT) is a widely used nitroaromatic explosive with significant detrimental effects on the environment and human health. Its detection is of great importance. In this study, both electrochemiluminescence (ECL)-based detection of TNT through the formation of a TNT-amine complex and the detection of TNT through electrochemiluminescence resonance energy transfer (ECRET) are developed for the first time. 3-Aminopropyltriethoxysilane (APTES)-modified [Ru(phen)(3)](2+) (phen=1,10-phenanthroline)-doped silica nanoparticles (RuSiNPs) with uniform sizes of (73 +/- 3)nm were synthesized. TNT can interact with APTES-modified RuSiNPs through charge transfer from electron-rich amines in the RuSiNPs to the electron-deficient aromatic ring of TNT to form a red TNT-amine complex. The absorption spectrum of this complex overlaps with the ECL spectrum of the APTES-modified RuSiNPs/triethylamine system. As a result, ECL signals of the APTES-modified RuSiNPs/triethylamine system are turned off in the presence of TNT owing to resonance energy transfer from electrochemically excited RuSiNPs to the TNT-amine complex. This ECRET method has been successfully applied for the sensitive determination of TNT with a linear range from 1x10(-9) to 1x10(-6)M with a fast response time within 1min. The limit of detection is 0.3nM. The method exhibits good selectivity towards 2,4-dinitrotoluene, p-nitrotoluene, nitrobenzene, phenol, p-quinone, 8-hydroxyquinoline, p-phenylenediamine, K-3[Fe(CN)(6)], Fe3+, NO3-, NO2-, Cr3+, Fe2+, Pb2+, SO32-, formaldehyde, oxalate, proline, and glycine.

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