1,3-Di-naphthalimide Conjugate of Calix[4]arene as a Sensitive and Selective Sensor for Trinitrophenol and This Turns Reversible when Hybridized with Carrageenan as Beads

Abstract

A fluorescent naphthalimide conjugate of calix[4]arene ( L 1 ) has been synthesized and characterized. The selective and efficient detection of trinitrophenol (TNP) by L 1 among nine other different nitroaromatic compounds was demonstrated using absorption and fluorescence spectroscopy. The minimum detection limit is 29 nM, which is the lowest reported so far by any conjugate of calixarene toward TNP. The fluorescence quenching is associated with a high Stern–Volmer constant of 3.3 ± 0.4 × 10 5 M –1 . The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) data revealed a network structure with pores having a weighted average size of 0.66 ± 0.08 μm for L 1 . When incubated with TNP, the pores were filled with fibril structures, as supported by both SEM and TEM data. In order to demonstrate the real time applications, the L 1 has been coated onto a Whatman filter paper and the imprint of TNP contaminated thumb has been detected upon physical contact. The 1 HNMR titration and the studies carried out using the control molecule support the necessity of both the naphthalimide moiety and the calixarene platform for sensing. In order to mend L 1 as a reversible sensor for TNP, the same is incorporated into carrageenan beads ( L 1 @ C b ) and the reversible sensing has been shown for three cycles by reusing the same material upon recovery followed by washing it. The solid-state detection of TNP has also been demonstrated using the lyophilized L 1 @ C b bead powder. The fluorescence intensity of L 1 was quenched upon addition of solid TNP to the lyophilized bead powder of L 1 @ C b as studied by fluorescence microscopy. The computational studies show that one of the arms of the calixarene takes a bent conformation, and the 1:1 TNP complex of L 1 is stabilized by exhibiting differential extents of hydrogen bonding interactions with the two arms owing to their conformational difference. The result of such complexation was already felt through the shifts observed in the experimentally measured 1 HNMR spectra.

A summary of calixarene-based fluorescent sensors developed during the past five years

“…Another calix [4]arene-based sensor 15 for TNP was synthesized by Narula et al, 47 bearing two naphthalimide units (L1) at the lower rim as binding sites and a fluorescent reporter (Fig. 9).…”