Highly sensitive and selective hyphenated technique (molecularly imprinted polymer solid-phase microextraction-molecularly imprinted polymer sensor) for ultra trace analysis of aspartic acid enantiomers

J Chromatogr A. 2013 Mar 29:1283:9-19. doi: 10.1016/j.chroma.2013.01.096. Epub 2013 Jan 31.

Abstract

The present work is related to combination of molecularly imprinted solid-phase microextraction and complementary molecularly imprinted polymer-sensor. The molecularly imprinted polymer grafted on titanium dioxide modified silica fiber was used for microextraction, while the same polymer immobilized on multiwalled carbon nanotubes/titanium dioxide modified pencil graphite electrode served as a detection tool. In both cases, the surface initiated polymerization was found to be advantageous to obtain a nanometer thin imprinted film. The modified silica fiber exhibited high adsorption capacity and enantioselective diffusion of aspartic acid isomers into respective molecular cavities. This combination enabled double preconcentrations of d- and l-aspartic acid that helped sensing both isomers in real samples, without any cross-selectivity and matrix complications. Taking into account 6×10(4)-fold dilution of serum and 2×10(3)-fold dilution of cerebrospinal fluid required by the proposed method, the limit of detection for l-aspartic acid is 0.031ngmL(-1). Also, taking into account 50-fold dilution required by the proposed method, the limit of detection for d-aspartic acid is 0.031ngmL(-1) in cerebrospinal fluid.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adsorption
  • Aspartic Acid / analysis*
  • Aspartic Acid / blood
  • Aspartic Acid / cerebrospinal fluid
  • Aspartic Acid / chemistry*
  • Chromatography, Liquid
  • Graphite / chemistry
  • Humans
  • Limit of Detection
  • Mass Spectrometry
  • Microscopy, Electron, Scanning
  • Molecular Imprinting / methods*
  • Nanotubes, Carbon / chemistry
  • Polymers / chemistry
  • Reproducibility of Results
  • Silicon Dioxide / chemistry
  • Solid Phase Microextraction / methods*
  • Stereoisomerism
  • Surface Properties

Substances

  • Nanotubes, Carbon
  • Polymers
  • Aspartic Acid
  • Silicon Dioxide
  • Graphite