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Preparation and characterization of a molecularly imprinted polymer by grafting on silica supports: a selective sorbent for patulin toxin

  • Dayun ZhaoEmail author
  • Jingfu Jia
  • Xuelei Yu
  • Xiangjun Sun
Original Paper

Abstract

A new molecularly imprinted polymer (MIP) has been prepared on silica beads using the radical “grafting from” polymerization method for selective extraction of minor contaminant mycotoxin of patulin (PTL). After the introduction of amino groups onto the silica surface with 3-aminopropyltriethoxysilane, azo initiator onto the silica surface was achieved by the reaction of surface amino groups with 4,4′-azobis(4-cyanopentanoic acid). The scale-up synthesis of MIP was then carried out in the presence of 6-hydroxynicotinic acid as template substitute, functional, and cross-linking monomers. The prepared sorbent was characterized using FT-IR spectroscopy, scanning electron microscopy, elemental analysis, and the adsorption–desorption selectivity, and the capacity characteristic of the polymer was investigated by a conventional batch adsorption test and Scatchard plot analysis. The results indicated that coated polymers had specific adsorption to PTL as compared with its co-occurring 5-hydroxymethyl-2-furaldehyde (hydroxymethylfurfural (HMF)), at the same bulk concentration for solution of PTL and HMF, the maximum absorbance in the solid-phase extraction (SPE) method to PTL were 93.97% or 0.654 μg/mg while to HMF they were 76.89% or 0.496 μg/mg. Scatchard analysis revealed that two classes of binding sites were formed in PTL-MIP with dissociation constants of 3.2 × 10−2 and 5.0 × 10−3 mg/mL and the affinity binding sites of 8.029 and 1.364 mg/g, respectively. The recoveries of PTL were more than 90% for the developed MISPE and around 75% for the traditional liquid–liquid extraction in spiked apple juice samples. It was concluded that the method is suitable for the scale-up synthesis of PTL-MIP grafted on silica, and the polymer can be effectively applied as SPE coupled with high-performance liquid chromatography (HPLC) for the determination of PTL in apple juice or other related products.

Figure

HPLC chromatograms of loading, washing, and eluting fractions of PTL and HMF from the MIP cartridge. Test samples in each chromatogram from top to bottom: mixed standard of HMF and PTL (10 mg/L), residue solution through the cartridge, first elution and second elution washed with 1 mL of 1% (w/v) HAc aqueous solution.

Keywords

Molecular imprinted polymers (MIPs) Patulin Mimic Grafting Silica 

Abbreviations used

AM

Acrylamide

ACPA

4,4′-Azobis(4-cyanopentanoic acid)

ACPC

4,4′-Azobis(4-cyanopentanoic acid) chlorides

AOAC

Association of Analytical Communities

APTS

3-Aminopropyltriethoxysilane

CA

Coumalic acid

DCC

Dicyclohexylcarbodiimide

DMAP

Dimethylamino pyridine

DMSO

Dimethyl sulfoxide

EA

Elemental analysis

EGDMA

Ethylene glycol dimethacrylate

FT-IR

Fourier transform infrared spectrometry

HMF

5-Hydroxymethyl furfural

2-HNA

2-Hydroxynicotinic acid

6-HNA

6-Hydroxynicotinic acid

HPLC

High-performance liquid chromatography

ITC

Isothermal titration calorimetry

LLE

Liquid–liquid extraction

LOD

Limits of detection

LOQ

Limits of quantification

MAA

Methacrylic acid

MIPs

Molecularly imprinted polymers

MISPE

Molecularly imprinted solid-phase extraction

MS

Mass spectrometry

NIPs

Non-template imprinted polymers

PAD

Photodiode array detector

PTL

Patulin

RSD

Relative standard deviation

SEM

Scanning electron microscope

SPE

Solid-phase extraction

Notes

Acknowledgment

We gratefully acknowledge financial support from the Science and Technology Commission of Shanghai Municipality, project no. 06DZ05128.

Supplementary material

216_2011_5282_MOESM1_ESM.pdf (58 kb)
Fig. S1 The Hyperchem-derived energy minimized structure of AM and PTL or analogues. The presence of hydrogen bonds is indicated by dashed lines. Nitrogen = green, carbon = red, oxygen = blue, hydrogen = black. (PDF 57.5 kb)

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Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Dayun Zhao
    • 1
    • 2
    Email author
  • Jingfu Jia
    • 1
  • Xuelei Yu
    • 1
  • Xiangjun Sun
    • 1
    • 2
  1. 1.Department of Food Science and Technology, School of Agriculture and BiologyShanghai Jiao Tong UniversityShanghaiChina
  2. 2.Bor S. Luh Food Safety Research CenterShanghai Jiao Tong UniversityShanghaiChina

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