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Detection of nitroaromatic explosives by 3D hyperbranched σ-π conjugate polymer on the basis of the POSS scaffold

Abstract

A three-dimensional hyperbranched polymer 3D-HPs with σ-π conjugated PDMPS (poly(dichloromethylphenylsilane)s) units covalently bonded to a POSS scaffold were prepared by a one-step “Thiol-ene Click chemistry” reaction. Compared with POSS-based organic polymers, 3D-HPs with flexible Si-Si chain showed better solubility. This 3D hyperbranched polymer exhibited outstanding thermal stability and high fluorescence quantum yield. As sensing materials for detecting nitroaromatics (NACs) in solution, 3D-HPs showed excellent sensibility (Ksv = 2.83 × 104 M−1) in the presence of TNT/THF (2,4,6-trinitrotoluene), indicating that super quenching effect may get involved in 3D-HPs. However, in another case of the 3D-HPs film exposed to saturated DNT vapor, exhibiting a high quenching efficiency (Qf) of 70% after 100 s and the fluorescence of 3D-HPs film was completely quenched (82%) for 300 s. The superior fluorescent quenching performance of 3D-HPs could be explained by the following theories: (i) hyperbranched conjugated polymers afford multi-dimensional transport pathways for excitons to migrate; (ii) high electron affinity and fast electron mobility of σ-π conjugated polysilane; (iii) the weak noncovalent interaction between electropositive δ+ Si atoms of σ-π conjugated polysilane and N and/ or O atoms of electron-deficient nitroaromatics (NACs), which could effectively absorb NACs. Furthermore, the fact that the steric hinderance of octathiol-POSS units in 3D-HPs could improve the permeability of the film sensor. This 3D hyperbranched σ-π conjugated polymer 3D-HPs had the potential to prepare sensitive, selective, and stable sensors for the detection of NACs explosives.

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Publication details

The article was received on 18 May 2017, accepted on 05 Jun 2017 and first published on 07 Jun 2017


Article type: Paper
DOI: 10.1039/C7TA04351A
Citation: J. Mater. Chem. A, 2017, Accepted Manuscript
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    Detection of nitroaromatic explosives by 3D hyperbranched σ-π conjugate polymer on the basis of the POSS scaffold

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

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