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Frontiers of Materials Science

Front. Mater. Sci.    2016, Vol. 10 Issue (2) : 178-186     DOI: 10.1007/s11706-016-0334-z
Temperature and anion responsive self-assembly of ionic liquid block copolymers coating gold nanoparticles
Junbo LI1,*(),Jianlong ZHAO2,Wenlan WU2,Ju LIANG1,Jinwu GUO1,Huiyun ZHOU1,Lijuan LIANG1
1. College of Chemical Engineering & Pharmaceutics, Henan University of Science & Technology, Luoyang 471023, China
2. Medical School, Henan University of Science & Technology, Luoyang 471003, China
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In this paper, double hydrophilic ionic liquid block copolymers (ILBCs), poly poly[1-methyl-3-(2-methacryloyloxy propylimidazolium bromine)]-block-(N-isopropylacrylamide) (PMMPImB-b-PNIPAAm) was first synthesized by reversible addition-fragmentation chain transfer (RAFT) and then attached on the surface of gold nanoparticles (Au NPs) via a strong gold-sulfur bonding for preparing hybrid nanoparticles (PMMPImB-b-PNIPAAm-@-Au NPs). The hybrid NPs had a three layers micelle-like structure, including a gold core, thermo-responsive inner shell and anion responsive outer corona. The self-assembling behavior of thermal- and anion-response from shell and corona were respectively investigated by change of temperature and addition of (CF3SO2)2N-. The results showed the hybrid NPs retained a stable dispersion beyond the lower critical solution temperature (LCST) because of the space or electrostatic protecting by outer PMMPImB. However, with increasing concentration of (CF3SO2)2N-, the micellization of self-assembling PMMPImB-b-PNIPAAm-@-Au NPs was induced to form micellar structure containing the core with hydrophobic PMMPImB-(CF3SO2)2N- surrounded by composite shell of Au NPs-PNIPAAm via the anion-responsive properties of ILBCs. These results indicated that the block copolymers protected plasmonic nanoparticles remain self-assembling properties of block copolymers when phase transition from outer corona polymer.

Keywords block?copolymer      dual stimuli-responsive      gold nanoparticles (Au NPs)      self-assembly     
Corresponding Authors: Junbo LI   
Online First Date: 05 April 2016    Issue Date: 11 May 2016
 Cite this article:   
Junbo LI,Jianlong ZHAO,Wenlan WU, et al. Temperature and anion responsive self-assembly of ionic liquid block copolymers coating gold nanoparticles[J]. Front. Mater. Sci., 2016, 10(2): 178-186.
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Junbo LI
Jianlong ZHAO
Wenlan WU
Jinwu GUO
Huiyun ZHOU
Lijuan LIANG
Fig.1  Scheme 1The schematic representation of preparing PMMPImB-b-PNIPAAm-Au NPs and its temperature and anion responsive self-assembly.
Fig.2  Scheme 2The schematic representation for synthesis of PMMPImB-CTA and PMMPImB-b-PNIPAAm.
Fig.3  1HNMR spectra of (A) PMMPImB-CTA and (B) PMMPImB-b-PNIPAAm in DMSO.
Fig.4  GPC traces of PMMPImB-CTA (A) and PMMPImB-b-PNIPAAm (B) in 8.5 g/L NaNO3 aqueous solution at room temperature.
Fig.5  (A) UV-vis spectrum, (B) TEM image and (C) DLS of PMMPImB-b-PNIPAAm-@-Au NPs. (D) TGA analysis of PMMPImB-b-PNIPAAm (a) and PMMPImB-b-PNIPAAm-@-Au NPs (b).
Fig.6  (A) The SPR peak and (B) responses of transmittance as a function of the concentration of (CF3SO2)2N- of PMMPImB-b-PNIPAAm-@-Au NPs. (C) The DLS result and (D) TEM image of the hybrid micelles solution forming at 0.2 mmol/L (CF3SO2)2N-.
Fig.7  (A) The SPR peak and (B) responses of transmittance of PMMPImB-b-PNIPAAm-@-Au NPs as a function of the temperature. (C) The DLS result and (D) TEM image of the PMMPImB-b-PNIPAAm-@-Au NPs at 42°C.
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