Issue 27, 2017

Detection of nitroaromatic explosives by a 3D hyperbranched σ–π conjugated polymer based on a POSS scaffold

Abstract

A three-dimensional hyperbranched polymer (3D-HP) with σ–π conjugated PDMPS (poly(dichloromethylphenylsilane)s) units covalently bonded to a polyhedral oligosilsesquioxane (POSS) scaffold was prepared by a one-step “thiol–ene click chemistry” reaction. Compared with POSS-based organic polymers, the 3D-HP with a flexible Si–Si chain showed enhanced solubility. This 3D hyperbranched polymer exhibited outstanding thermal stability and optimal photophysical properties. For probing nitroaromatics (NACs), the 3D-HP showed excellent sensitivity (Ksv = 2.83 × 104 M−1) against the presence of a tetrahydrofuran (THF) solution of 2,4,6-trinitrotoluene (TNT). In addition, the 3D-HP coated on glass films exposed to saturated DNT vapor exhibited a high quenching efficiency (ηEP) of the fluorescence of 3D-HP film, which was drastically suppressed (82%) for 300 s. The excellent fluorescent quenching performance of the 3D-HP can be attributed to the following points: (i) hyperbranched conjugated polymers afford multi-dimensional transport pathways for excitons migration; (ii) there exists in the polymer high electron affinity and rapid electron delocalization of σ–π conjugated polysilanes; (iii) noncovalent interactions between the electropositive δ+ Si atoms of σ–π conjugated polysilanes and N and/or O atoms of electron-deficient nitroaromatics (NACs) facilitate the adsorption of NACs. Furthermore, the bulky octathiol-POSS units in the 3D-HP can improve the permeability of the film sensor. This 3D hyperbranched σ–π conjugated polymer 3D-HP has the potential to be used to prepare sensitive, selective, and stable sensors for the detection of NACs explosives.

Graphical abstract: Detection of nitroaromatic explosives by a 3D hyperbranched σ–π conjugated polymer based on a POSS scaffold

Supplementary files

Article information

Article type
Paper
Submitted
18 May 2017
Accepted
05 Jun 2017
First published
07 Jun 2017

J. Mater. Chem. A, 2017,5, 14343-14354

Detection of nitroaromatic explosives by a 3D hyperbranched σ–π conjugated polymer based on a POSS scaffold

X. Ma, F. Tao, Y. Zhang, T. Li, F. M. Raymo and Y. Cui, J. Mater. Chem. A, 2017, 5, 14343 DOI: 10.1039/C7TA04351A

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