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Preparation of silica-based surface-imprinted core–shell nanoadsorbents for the selective recognition of sulfamethazine via reverse atom transfer radical precipitation polymerization

  • Tianbian Zou
  • Zhiping Zhou
  • Jiangdong Dai
  • Lin Gao
  • Xiao Wei
  • Chunxiang Li
  • Weixing Guan
  • Yongsheng Yan
Original Paper

Abstract

In this work, core–shell-structured silica-based surface molecularly imprinted nanoadsorbents (SMIPs) were prepared using a facile and general method that combined reverse atom transfer radical precipitation polymerization (RATRPP) and a surface imprinting nanotechnique. The resulting nanoadsorbents were then used to improve selective recognition and achieve the rapid removal of sulfamethazine (SMZ) from water. A modified one-step Stöber method was used to prepare monodisperse vinyl-functionalized silica spheres 250 nm in size. Subsequently, an imprinted polymer nanoshell (only 25 nm thick) was uniformly coated onto the surfaces of the hybrid silica spheres in a two-step polymerization process. The characteristics (i.e., isotherms, kinetics, and mechanism) of the adsorption of SMZ onto SMIPs from aqueous solution were systematically studied using batch experiments. The adsorption capacity increased with increasing initial concentration and contact time. The nonlinear Langmuir, Freundlich, and Temkin models were used to analyze equilibrium data, and these data were found to be best represented by the Langmuir isotherm, which yielded a high maximum monolayer adsorption capacity of 76.34 μmol g−1 due to the effective sites located in the thin imprinted nanoshell. The adsorption process rapidly reached equilibrium and the data were best described by a pseudo-second-order rate model. The adsorption mechanism was mainly governed by intraparticle diffusion. The SMIPs adsorbed more SMZ than nonimprinted nanoadsorbents did, and they adsorbed much more of the template than other antibiotics, suggesting that the SMIPs show excellent selective recognition. Reusable SMIPs were shown to be a potentially efficient nanoadsorbent for the selective and fast removal of antibiotic residues from aqueous environments.

Keywords

Surface-imprinted nanoadsorbents Sulfamethazine residues Selective recognition RATRPP Core–shell structure 

Abbreviations

MIPs

Molecularly imprinted polymers

SMIPs

Silica-based surface molecularly imprinted nanoadsorbents

CRP

Controlled/living radical polymerization

RATRP

Reverse atom transfer radical polymerization

RATRPP

Reverse atom transfer radical precipitation polymerization

MPS

3-Methacryloxypropyl trimethoxysilane

VTES

Vinyltriethoxysilane

4-VP

4-Vinylpyridine

EGDMA

Ethylene glycol dimethacrylate

AIBN

Azobisisobutyronitrile

SMZ

Sulfamethazine

CFX

Ciprofloxacin

TC

Tetracycline

FT-IR

Fourier transform infrared spectra

SEM

Scanning electron microscope

TGA

Thermogravimetric analysis

TEM

Transmission electron microscope

Notes

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (nos. 21176107, 21174057, 21107037, and 21277063), the National Basic Research Program of China (973 Program, 2012CB821500), Natural Science Foundation of Jiangsu Province (BK2011459), Ph.D. Innovation Programs Foundation of Jiangsu Province (no. CXZZ13_0668), Research Fund for the Doctoral Program of Higher Education of China (20110205110014), and Jiangsu Planned Projects for Postdoctoral Research Funds (1102119C).

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Copyright information

© Springer Science+Business Media Dordrecht 2014

Authors and Affiliations

  • Tianbian Zou
    • 1
  • Zhiping Zhou
    • 1
  • Jiangdong Dai
    • 1
  • Lin Gao
    • 2
  • Xiao Wei
    • 1
  • Chunxiang Li
    • 1
  • Weixing Guan
    • 3
  • Yongsheng Yan
    • 2
  1. 1.School of Material Science and EngineeringJiangsu UniversityZhenjiangChina
  2. 2.School of Chemistry and Chemical EngineeringJiangsu UniversityZhenjiangChina
  3. 3.College of Environmental Science and EngineeringChang’an UniversityXi’anChina

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