Citation: HE Qiangfang, WU Yinghong, CAI Zhijian, XIE Wang. Synthesis of Fluorescent Cross-linked Stabilized Polymeric Micelles Based on Salicylidene Schiff Base/Zn²⁺ Complexes and Sensor for Cu²⁺ Detection[J]. Chinese Journal of Applied Chemistry, ;2016, 33(6): 701-709. doi: 10.11944/j.issn.1000-0518.2016.06.150413 shu

Synthesis of Fluorescent Cross-linked Stabilized Polymeric Micelles Based on Salicylidene Schiff Base/Zn²⁺ Complexes and Sensor for Cu²⁺ Detection

HE Qiangfang ^a,b,c,, ,
WU Yinghong ^a ,
CAI Zhijian ^a ,
XIE Wang ^a

1.
a Department of Chemistry, Guangdong University of Education, Guangzhou 510303, China;
2.
b State Key Laboratory of Medicinal Chemical Biology, Nankai University, Tianjin 300071, China;
3.
c State Key Laboratory of Molecular Engineering of Polymers, Fudan University, Shanghai 200433, China

Corresponding author: HE Qiangfang,
Received Date: 24 November 2015
Available Online: 28 December 2015
Fund Project:

A well-defined polymer with pendant salicylaldehyde groups(PHVB) was achieved by reversible addition-fragmentation chain transfer(RAFT) polymerization with S-1-dodecyl-S'-(α,α'-dimethyl-α"-acetic acid) trithiocarbonate as the RAFT agent and a salicylaldehyde-functionalized vinyl monomer, 2-hydroxy-5-vinylbenzaldehyde(HVB) in THF at 65℃. The resulting well-defined polymer with pendant salicylaldehyde groups can react directly with monoamine-terminated PEG(PEG-NH₂, number-average relative molecular mass 2000 g/mL, 0.5 stoichiometric number of the -CHO group in PolyHVB) to afford an amphiphilic graft copolymer bearing a pendant salicylidene Schiff base PHVB-graft-PEG with 50% grafting density. These new polymers were characterized by GPC and ¹HNMR. Owing to the presence of hydrophilic PEG pendants, PHVB-graft-PEG is capable of self-assembling into nano-sized micelles with salicylidene Schiff base functioned cores, PEG coronas in ethanol. Coordination of the pre-assembled PHVB-graft-PEG micelles with Zn(OAc)₂ will endow the polymeric micelles with fluorescence features, and simultaneously the resulting luminescent micelles may be stabilized by ionic cross-linking in consequence of the complex reaction at the core. Thus, the luminescence properties and form of the obtained micelles were investigated by UV-Vis spectra(UV-Vis), fluorescence spectra(FLL), dynamic light scattering(DLS), transmission electron microscopy(TEM).After removing ethanol by drying, the resultant Zn²⁺ coordinated particles can be re-dispersed readily in water or common organic solvent to form a micellar solution, which display blue fluorescence with maximum emission peak around 460 nm, indicating the same aggregate size(nearly 100 nm) as before re-dispersion. The obtained luminescent nanoparticles can be used as a highly selective fluorescent probe for Cu²⁺ ion over other metal ions such as Cd^{2 +}, Mg²⁺, Ni²⁺, Pb²⁺, Ca²⁺, Hg²⁺, Al³⁺, Mn²⁺ in aqueous solution, and exhibit a linear range of 0~50 μmol/L and detection limit of 0.05 μmol/L Cu²⁺, respectively.
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Synthesis of Fluorescent Cross-linked Stabilized Polymeric Micelles Based on Salicylidene Schiff Base/Zn2+ Complexes and Sensor for Cu2+ Detection

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通讯作者: 陈斌, bchen63@163.com

Synthesis of Fluorescent Cross-linked Stabilized Polymeric Micelles Based on Salicylidene Schiff Base/Zn²⁺ Complexes and Sensor for Cu²⁺ Detection