Improved sensing strategies are needed for facile, accurate and rapid detection of aromatic and nonaromatic explosives. Density functional theory was used to evaluate the relative binding interaction energies between halogen-containing sensor model molecules and nitro-containing explosives. Interaction energies ranged from –18 to –14 kJ/mol and highly directional halogen bonding interactions were observed with bond distances ranging between 3.0 and 3.4 Å. In all geometry optimized structures, the sigma-hole of electropositive potential on the halogen aligned with a lone pair of electrons on the nitro-moiety of the explosive. The computational results predict that the strongest interactions will occur with iodine-based sensors as, of all the halogens studied, iodine is the largest, most polarizable halogen with the smallest electronegativity. Based on these promising proof-of-concept results, synthetically accessible sensors were designed using1, 4-dihalobenzene (X= Cl, Br and I) with and without tetra-fluoro electron withdrawing groups attached to the benzene ring. These sensing molecules were embedded onto single walled carbon nanotubes that were mechanically abraded onto interdigitated array electrodes and these were used to measure the responses to explosive model compounds cyclohexanone and dimethyl-dinitro-benzene in nitrogen gas. Amperometric current-time curves for selectors and control molecules, including concentration correlated signal enhancement, as well as response and recovery times, indicate selector responsiveness to these model compounds, with the largest response observed for iodo-substituted sensors.
Copyright © 2019 American Chemical Society Cite this: ACS Sens. 2019, 4, 2, 389–397 Publication Date: January 23, 2019 https://doi.org/10.1021/acssensors.8b01246 Please note that downloads of the article are for private/personal use only.
A. K .A Jaini, M. K. Kitimet,* L. B. Hughes, K. J. Ulep, M. C. Leopold, and C. A. Parish, “Halogen Bonding Interactions for Aromatic and Non-Aromatic Explosive Detection,” ACS Sensors 2019 4 (2), 389-397. DOI: 10.1021/acssensors.8b01246.