Citation: Li Hua, Wu Xiao-fu, Hang Hao, Chen Yong-hong, Tong Hui, Wang Li-xiang. Water-dispersed Hyperbranched Conjugated Polymer Nanoparticles for Highly Sensitive Fluorescent Detection of Picric Acid[J]. Acta Polymerica Sinica, ;2018, (2): 248-256. doi: 10.11777/j.issn1000-3304.2018.17194 shu

Water-dispersed Hyperbranched Conjugated Polymer Nanoparticles for Highly Sensitive Fluorescent Detection of Picric Acid

Li Hua ^1,2 ,
Wu Xiao-fu ¹ ,
Hang Hao ^1,2 ,
Chen Yong-hong ^1,2 ,
Tong Hui ^1,, ,
Wang Li-xiang ^1,,

1.
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022
2.
University of Chinese Academy of Sciences, Beijing 100049

Corresponding author: Tong Hui, chemtonghui@ciac.ac.cn Wang Li-xiang, lixiang@ciac.an.cn
Received Date: 21 July 2017
Revised Date: 16 August 2017

Water-dispersed hyperbranched conjugated polymer nanoparticles (HCPN-QA) with quaternary ammonium salt as terminal groups were prepared by Suzuki polymerization in miniemulsion, followed by post-functionalization reaction, for highly sensitive and selective sensing of picric acid (PA) in aqueous solutions. By taking advantage of the positively charged quaternary ammonium salt terminal groups and hydrophobic cavities inside the hyperbranched core, bright blue emissive HCPN-QA can efficiently bind with PA in water by electrostatic attraction and hydrophobic encapsulation interaction, leading to highly efficient fluorescence quenching. The quenching constant of HCPN-QA was 6.36×10⁷ L/mol, which was three orders higher than that of its organic solution-dispersed hyperbranched conjugated polymer nanoparticle analogue (HCPN-OMe). HCPN-QA was capable of sensing PA in water with a detection limit of 7.8×10^-10 mol/L (0.18 μg/L), which was four orders of magnitude lower than that of HCPN-OMe (0.34 mg/L). Meanwhile, this value was also lower than the maximum permissible level (1 μg/L) for PA in drinking water set by World Health Organization (WHO). Moreover, by decreasing the amount of surfactants during the polymerization, nanoparticles with small diameter were obtained for further studying the relationship between particle size and the sensitivity for PA sensing. The fluorescent titration study indicated that particle size of HCPN-QA had little effect on the sensitivity for PA sensing. Furthermore, by combining electrostatic attraction and hydrophobic encapsulation interaction, HCPN-QA also showed much higher fluorescence quenching response to PA over other analytes, including 2, 4, 6-trinitrotoluene (TNT), 2, 4-dinitrotoluene (DNT), nitrobenzene, cyclotetramethylenetetranitramine (HMX), 1, 3, 5-trinitro-1, 3, 5-triazinane (RDX), nitromethane, ammonium nitrate, chlorobenzene, toluene and phenol in water. Especially, HCPN-QA showed nearly 60-fold higher quenching constant for PA than that of TNT, indicating that HCPN-QA had not only a high sensitivity, but also a good selectivity for PA sensing. In addition, contact mode detection was further performed using fluorescent paper strips based on HCPN-QA for naked eye detection of PA with a detection limit of 66 pg/mm².
- Hyperbranched conjugated polymer,
- Nanoparticle,
- Fluorescentsensor,
- Picric acid,
- Sensitive detection
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