Supramolecular Sensing of 2,4,6-Trinitrophenol by a Tetrapyrenyl Conjugate of Calix[4]arene: Applicability in Solution, in Solid State, and on the Strips of Cellulose and Silica Gel and the Image Processing by a Cellular Phone.

Abstract

A calix[4]arene conjugate possessing a tetrapyrenyl moiety at its upper rim (R) is designed as a receptor for sensing trinitrophenol (TNP). To understand the role of the calix[4]arene platform and that of pyrenyl moieties in R, two other control molecules were synthesized. These are as follows: the one possessing a tetraphenyl moiety in place of tetrapyrenyl (R1) and the other one is a p-pyrenyl-hydroxy benzene (R2) that is devoid of the calix[4]arene platform. The R shows high sensitivity toward TNP in tetrahydrofuran (THF) over eleven other nitroaromatic compounds (NACs) studied by exhibiting large fluorescence enhancement and hence is selective to TNP over the other NACs studied. However, the control molecules R1 and R2 showed only marginal fluorescence enhancement, supporting the need of a calixarene platform and the presence of a tetrapyrenyl moiety in the receptor system for the selective sensing of TNP. Further, R1 and R2 are not suitable for sensing, since these exhibit similar fluorescence response over several NACs studied. The binding of TNP by R has been addressed by fluorescence titration and isothermal titration calorimetry. The nature of the complexation of TNP by R has been revealed by the computational calculations, wherein the data showed the entrapment of TNP by two adjacent pyrene moieties via π–π stacking interactions. Such host–guest complexation is expected to restrict the mobility of the pyrene moieties present in R. The reduction of the flexibility of the pyrenyl moieties of R upon TNP binding is evidenced by the 1H NMR spectral study, wherein this acts as an additional evidence for the complexation. In the present study, the sensing of TNP by R has been shown in THF solution, on the surface of silica gel and the cellulose paper to result in lowest detection limits (LODs) of 1.5, 3.5, and 6.5 μM, respectively. Even the solid mixture of R and TNP showed LOD of 2.1 μmol. Since R is expected to show supramolecular aggregation that is dependent on the guest species, the corresponding details were probed by microscopy techniques, using scanning electron microscopy, atomic force microscopy, and transmission electron microscopy methods, and significant changes in the aggregation of R upon interaction with TNP were found. Such aggregation is responsible for the observed fluorescence enhancement. Thus, the tetrapyrenyl calix[4]arene conjugate (R) acts as a sensitive and robust platform for selective detection of TNP from a mixture of nitroaromatic compounds (NACs) wherein the fluorescence intensities can be imaged and managed by a cellular phone.