Metal enhanced fluorescence assay-based sensitive detection of a neurotoxic organophosphates pesticide, Paraoxon, is reported. The experimental approach involves the bio-interfacing of organophosphorus hydrolase with a high quantum yield fluorophore, pyranine (8-hydroxyl pyrene-1,3,6-trisulfonic acid trisodium salt), followed by the conjugation of the OPH-pyranine derivative with silica-coated silver nanoparticles (Ag NPs). The above bio-nanoprobe was used for the analysis of the organophosphate pesticide, wherein the induced hydrolysis of the pesticide cause the decrease in pH in the vicinity. An excitation light of 460 nm wavelength was used to monitor the changes in the resulting emission (at 510 nm) with respect to the changing pesticide concentrations (1–100 ppb). The introduction of the silica-coated AgNPs into the nanoprobe system was observed to deliver metal enhanced effect, leading to almost10-fold intensification of the fluorescence signal. The enhanced fluorescence assay format offers linear detection of Paraoxon in the concentration range of 1–100 ng mL−1 with the limit of detection 1 ng mL−1 (1 ppb).
This is a preview of subscription content, access via your institution.
Buy single article
Instant access to the full article PDF.
Price excludes VAT (USA)
Tax calculation will be finalised during checkout.
Chambers, J. E., & Levi, P. E. (1992). Organophosphates: Chemistry, fate, and effects (pp. 3–18). New York: Academic.
Munnecke, D. M. (1980). Enzymatic detoxification of waste organophosphate pesticides. Journal of Agricultural and Food Chemistry, 28, 105–111.
Leon-Gonzalez, M. E., & Townshend, A. (1990). Flow-injection determination of paraoxon by inhibition of immobilized acetylcholinesterase, A. Analytica Chimica Acta, 236, 267–272.
Mendoza, C. E. (1981). Thin-layer chromatography. In K. G. Dumas (Ed.), Pesticide analysis (pp. 1–44). New York: Marcel Dekker.
Das, K. G., & Kulkarni, P. S. (1981). Gas-liquid chromatography. In K. G. Dumas (Ed.), Pesticide analysis. New York: Marcel Dekker.
Hanks, A. R., & Colvin, B. M. (1981). High-performance liquid chromatography. In K. G. Dumas (Ed.), Pesticide analysis (pp. 99–174). New York: Marcel Dekker.
Barcelo, D., & Lawrence, J. F. (1992). Residue analysis of organophosphorus pesticides. In T. Charins & J. Sherma (Eds.), Emerging strategies for pesticide analysis (pp. 127–150). Boca Raton: CRC Press.
Liu, N., Cai, X., Lei, Y., Zhang, Q., Chan-Park, M. B., Li, C., et al. (2007). Single-walled carbon nanotube based real-time organophosphate detector. Electroanalysis 19, 616–619.
Aslan, K., Gryczynski, I., Malicka, J., Matveeva, E., Lakowicz, J. R., Geddes, C. D. (2005). Metal-enhanced fluorescence: an emerging tool in biotechnology. Current Opinion in Biotechnology, 16, 55–62.
Aslan, K., Leonenko, Z., Lakowicz, J., Geddes, C. (2005). Annealed silver-island films for applications in metal-enhanced fluorescence: interpretation in terms of radiating plasmons. Journal of Fluorescence, 15, 643–654.
Aslan, K., Wu, M., Lakowicz, J. R., Geddes, C. D. (2007). Fluorescent core−shell Ag@SiO2 nanocomposites for metal-enhanced fluorescence and single nanoparticle sensing platforms. Journal of the American Chemical Society, 129, 1524–1525.
Bahadur, N. M., Furusawa, T., Sato, M., Kurayama, F., Siddiquey, I. A., Suzuki, N. (2011). Fast and facile synthesis of silica coated silver nanoparticles by microwave irradiation. Journal of Colloid and Interface Science, 355, 312–320.
Cañamares, M. V., Garcia-Ramos, J. V., Gómez-Varga, J. D., Domingo, C., Sanchez-Cortes, S. (2005). Comparative study of the morphology, aggregation, adherence to glass, and surface-enhanced Raman scattering activity of silver nanoparticles prepared by chemical reduction of Ag+ using citrate and hydroxylamine. Langmuir, 21, 8546–8553.
Derkachova, A., & Kolwas, K. (2007). Size dependence of multipolar plasmon resonance frequencies and damping rates in simple metal spherical nanoparticles. The European Physical Journal Special Topics, 144, 93–99.
El Rassy, H., & Pierre, A. C. (2005). NMR and IR spectroscopy of silica aerogels with different hydrophobic characteristics. Journal of Non-Crystalline Solids, 351, 1603–1610.
Frančič, N., Košak, A., Lyagin, I., Efremenko, E., Lobnik, A. (2011). His6-OPH enzyme-based bio-hybrid material for organophosphate detection. Analytical and Bioanalytical Chemistry, 401, 2631–2638.
Geddes, C., & Lakowicz, J. (2002). Editorial: metal-enhanced fluorescence. Journal of Fluorescence, 12, 121–129.
Innocenzi, P., Falcaro, P., Grosso, D., Babonneau, F. (2003). Order−disorder transitions and evolution of silica structure in self-assembled mesostructured silica films studied through FTIR spectroscopy. The Journal of Physical Chemistry. B, 107, 4711–4717.
Ji, X., Zheng, J., Xu, J., Rastogi, V. K., Cheng, T. C., DeFrank, J. J., et al. (2005). (CdSe) ZnS quantum dots and organophosphorus hydrolase bioconjugate as biosensors for detection of Paraoxon. The Journal of Physical Chemistry. B, 109, 3793–3799.
Kirk, C. T. (1988). Quantitative analysis of the effect of disorder-induced mode coupling on infrared absorption in silica. Physical Review B, 38, 1255–1273.
Kobayashi, Y., Katakami, H., Mine, E., Nagao, D., Konno, M., Liz-Marzán, L. M. (2005). Silica coating of silver nanoparticles using a modified Stöber method. Journal of Colloid and Interface Science, 283, 392–396.
Lakowicz, J. R., Malicka, J., D’Auria, S., Gryczynski, I. (2003). Release of the self-quenching of fluorescence near silver metallic surfaces. Analytical Biochemistry, 320, 13–20.
Lu, H. W., Liu, S. H., Wang, X. L., Qian, X. F., Yin, J., Zhu, Z. K. (2003). Silver nanocrystals by hyperbranched polyurethane-assisted photochemical reduction of Ag+. Materials Chemistry and Physics, 81, 104–107.
Lukomska, J., Malicka, J., Gryczynski, I., Leonenko, Z., Lakowicz, J. R. (2005). Fluorescence enhancement of fluorophores tethered to different sized silver colloids deposited on glass substrate. Biopolymers, 77, 31–37.
Malicka, J., Gryczynski, I., Kusba, J., Lakowicz, J. R. (2003). Effects of metallic silver island films on resonance energy transfer between N, N′-(dipropyl)-tetramethyl- indocarbocyanine (Cy3)- and N, N′-(dipropyl)-tetramethyl- indodicarbocyanine (Cy5)-labeled DNA. Biopolymers, 70, 595–603.
Marty, J. L., Sode, K., Karube, I. (1992). Biosensor for detection of organophosphate and carbamate insecticides. Electroanalysis, 4, 249–252.
Mukherjee, P., Ahmad, A., Mandal, D., Senapati, S., Sainkar, S. R., Khan, M. I., et al. (2001). Fungus-mediated synthesis of silver nanoparticles and their immobilization in the mycelial matrix: A novel biological approach to nanoparticle synthesis. Nano Letters, 1, 515–519.
Patra, A., Sominska, E., Ramesh, S., Koltypin, Y., Zhong, Z., Minti, H., et al. (1999). Sonochemical preparation and characterization of Eu2O3 and Tb2O3 doped in and coated on silica and alumina nanoparticles. The Journal of Physical Chemistry. B, 103, 3361–3365.
Ray, K., Badugu, R., Lakowicz, J. R. (2006). Metal-enhanced fluorescence from CdTeNanocrystals: a single-molecule fluorescence study. Journal of the American Chemical Society, 128, 8998–8999.
Smitha, S. L., Nissamudeen, K. M., Philip, D., Gopchandran, K. G. (2008). Studies on surface plasmon resonance and photoluminescence of silver nanoparticles. SpectrochimicaActa Part A: Molecular and Biomolecular Spectroscopy, 71, 186–190.
Stöber, W., Fink, A., Bohn, E. (1968). Controlled growth of monodisperse silica spheres in the micron size range. Journal of Colloid and Interface Science, 26, 62–69.
Brinker, C. J. & Scherer, G.W. (1990). Sol-gel Science: The Physics and Chemistry of Sol-gel Processing. San Diego: Gulf Professional Publishing.
The authors gratefully acknowledge the support of the director, CSIR-CSIO, Chandigarh. One of the authors (Satish K Tuteja) thanks CSIR, New Delhi, India for granting senior research fellowship.
Electronic supplementary material
Below is the link to the electronic supplementary material.
(DOCX 286 kb)
About this article
Cite this article
Tuteja, S.K., Kukkar, M., Kumar, P. et al. Synthesis and Characterization of Silica-Coated Silver Nanoprobe for Paraoxon pesticide Detection. BioNanoSci. 4, 149–156 (2014). https://doi.org/10.1007/s12668-014-0129-6