Chem. Mater., 20 (8), 28292838, 2008. 10.1021/cm703641s
Web Release Date: March 21, 2008

Copyright © 2008 American Chemical Society

One- and Two-Photon Fluorescent Polyhedral Oligosilsesquioxane (POSS) Nanosensor Arrays for the Remote Detection of Analytes in Clouds, in Solution, and on Surfaces

Claire Hartmann-Thompson,* Douglas L. Keeley, Kathleen M. Pollock, Petar R. Dvornic, Steven E. Keinath, Marcos Dantus, Tissa C. Gunaratne, and Dale J. LeCaptain§

Michigan Molecular Institute, 1910 West St. Andrews Road, Midland, Michigan 48640-2696, Department of Chemistry, Michigan State University, East Lansing, Michigan 48824-1322, and Department of Chemistry, Central Michigan University, Mount Pleasant, Michigan 48859

Received December 20, 2007

Revised Manuscript Received January 30, 2008

Abstract:

A series of polyhedral oligosilsesquioxane (POSS) nanosensors functionalized with fluorophores that change their wavelength of emission in response to their chemical environment has been synthesized and characterized by IR, NMR, UV, one- and two-dimensional fluorescence spectroscopy, MALDI-TOF MS, and electrospray MS. When each nanosensor in an array of n nanosensors is functionalized with a different wavelength shifting fluorophore, the array can generate a unique fingerprint comprised of n emission wavelength data points in response to a given chemical warfare agent (CWA) simulant or toxic industrial chemical (TIC). One-photon fluorescence fingerprints were constructed by measuring the fluorescence spectra of nanosensor−analyte pairs in solution. Two-photon fluorescence fingerprints were then generated by remotely interrogating nanosensor−analyte pairs using a femtosecond IR laser and a stand-off fluorimeter. Two-photon fingerprints were obtained for analytes in solution, on a surface, and in cloud form. A four-component nanosensor array could differentiate a homologous series of alcohols and distinguish G and VX classes of nerve agent simulants.

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