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Speciation analysis of aqueous nanoparticulate diclofenac complexes by solid-phase microextraction.

Katarzyna Zielińska1, Herman P van Leeuwen, Sylvain Thibault

  • 1Laboratory of Physical Chemistry and Colloid Science, Wageningen University, Dreijenplein 6, 6703 HB Wageningen, The Netherlands.

Langmuir : the ACS Journal of Surfaces and Colloids
|September 20, 2012
PubMed
Summary

Nanoparticles (NPs) enhance the sorption rate of diclofenac, a pharmaceutical, by acting as a shuttle. This study reveals that only the neutral form of diclofenac binds, with NP-bound forms remaining labile during solid-phase microextraction (SPME).

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Area of Science:

  • Environmental Chemistry
  • Analytical Chemistry
  • Materials Science

Background:

  • Understanding the dynamic sorption of organic compounds by nanoparticles (NPs) is crucial for environmental and pharmaceutical applications.
  • Diclofenac, a common pharmaceutical, interacts with various environmental matrices, including NPs.
  • Solid-phase microextraction (SPME) is a widely used technique for analyzing organic compounds in complex matrices.

Purpose of the Study:

  • To analyze the dynamic sorption of diclofenac by impermeable (silica, SiO(2)) and permeable (bovine serum albumin, BSA) nanoparticles using SPME.
  • To elucidate the role of NPs in the sorption kinetics and partition equilibrium of diclofenac.
  • To determine the lability of NP-bound diclofenac species on the effective time scale of SPME.

Main Methods:

  • Solid-phase microextraction (SPME) was employed to study diclofenac sorption.
  • Experiments were conducted using dispersions of silica (SiO(2)) and bovine serum albumin (BSA) nanoparticles.
  • Kinetic and thermodynamic parameters, including the desorption rate constant (k(des)), were derived.

Main Results:

  • Only the protonated neutral form of diclofenac accumulates in the solid phase, governing the partition equilibrium.
  • The presence of SiO(2) and BSA nanoparticles significantly enhances the rate of solid/water partition equilibration.
  • NP-bound diclofenac species exhibit labile behavior, with a desorption rate constant (k(des)) sufficiently high for the SPME time scale.

Conclusions:

  • Nanoparticles act as a shuttle, enhancing the diffusive supply of diclofenac to the water/solid interface and accelerating equilibration.
  • The sorption dynamics are controlled by the coupled diffusion of neutral, deprotonated, and NP-bound diclofenac species.
  • The findings provide quantitative insights into the behavior of pharmaceuticals in NP-containing environmental systems.