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Zeitschrift für Physikalische Chemie

International journal of research in physical chemistry and chemical physics

Editor-in-Chief: Rademann, Klaus

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Volume 232, Issue 5-6


Influence of Organic Ligands on the Surface Oxidation State and Magnetic Properties of Iron Oxide Particles

Christian Goroncy
  • Institut für Chemie und Biochemie – Physikalische und Theoretische Chemie, Freie Universität Berlin, Berlin, Germany
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/ Patrick E. J. Saloga
  • Institut für Chemie und Biochemie – Physikalische und Theoretische Chemie, Freie Universität Berlin, Berlin, Germany
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/ Mathias Gruner
  • Institut für Chemie und Biochemie – Physikalische und Theoretische Chemie, Freie Universität Berlin, Berlin, Germany
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/ Madlen Schmudde
  • Institut für Chemie und Biochemie – Physikalische und Theoretische Chemie, Freie Universität Berlin, Berlin, Germany
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/ Jonathan Vonnemann
  • Institut für Chemie und Biochemie – Organische Chemie, Freie Universität Berlin, Berlin, Germany
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/ Edwige Otero / Rainer Haag
  • Institut für Chemie und Biochemie – Organische Chemie, Freie Universität Berlin, Berlin, Germany
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/ Christina Graf
  • Corresponding author
  • Institut für Chemie und Biochemie – Physikalische und Theoretische Chemie, Freie Universität Berlin, Berlin, Germany
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Published Online: 2018-04-13 | DOI: https://doi.org/10.1515/zpch-2017-1084


For the application of iron oxide nanoparticles from thermal decomposition approaches as contrast agents in magnetic resonance imaging (MRI), their initial hydrophobic ligands have to be replaced by hydrophilic ones. This exchange can influence the surface oxidation state and the magnetic properties of the particles. Here, the effect of the anchor group of three organic ligands, citric acid and two catechols, dihydrocaffeic acid and its nitrated derivative nitro dihydrocaffeic acid on iron oxide nanoparticles is evaluated. The oleate ligands of Fe3O4/γ-Fe2O3 nanoparticles prepared by the thermal decomposition of iron oleate were exchanged against the hydrophilic ligands. X-ray absorption spectroscopy, especially X-ray magnetic circular dichroism (XMCD) measurements in the total electron yield (TEY) mode was used to investigate local magnetic and electronic properties of the particles’ surface region before and after the ligand exchange. XMCD was combined with charge transfer multiplet calculations which provide information on the contributions of Fe2+ and Fe3+ at different lattice sites, i.e. either in tetrahedral or octahedral environment. The obtained data demonstrate that nitro hydrocaffeic acid leads to least reduction of the magnetizability of the surface region of the iron oxide nanoparticles compared to the two other ligands. For all hydrophilic samples, the proportion of Fe3+ ions in octahedral sites increases at the expense of the Fe2+ in octahedral sites whereas the percentage of Fe3+ in tetrahedral sites hardly changes. These observations suggest that an oxidation process took place, but a selective decrease of the Fe2+ ions in octahedral sites ions due to surface dissolution processes is unlikely. The citrate ligand has the least oxidative effect, whereas the degree of oxidation was similar for both catechol ligands regardless of the nitro group. Twenty-four hours of incubation in isotonic saline has nearly no influences on the magnetic properties of the nanoparticles, the least on those with the nitrated hydrocaffeic acid ligand.

Keywords: iron oxide nanoparticles; surface oxidation; X-ray absorption spectroscopy; X-ray magnetic circular dichroism (XMCD)

Dedicated to: Eckart Rühl on the occasion of his 60th birthday.


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About the article

aFachbereich Chemie- und Biotechnologie, Hochschule Darmstadt – University of Applied Sciences, Darmstadt, Germany.

Received: 2017-11-28

Accepted: 2018-03-09

Published Online: 2018-04-13

Published in Print: 2018-05-24

Citation Information: Zeitschrift für Physikalische Chemie, Volume 232, Issue 5-6, Pages 819–844, ISSN (Online) 2196-7156, ISSN (Print) 0942-9352, DOI: https://doi.org/10.1515/zpch-2017-1084.

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