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Adduct formation of ionic and nanoparticular silver with amino acids and glutathione

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Abstract

To investigate the interaction of ionic and nanoparticular silver with amino acids and small peptides, an electrospray ionization time-of-flight mass spectrometry method was developed. Monomeric and oligomeric silver adducts were formed with amino acids including cysteine (Cys), methionine, histidine, lysine, or the tripeptide glutathione (GSH). The obtained spectra for ionic silver show clusters in different ratios between Ag+ and the reaction partners (X) including [Ag n X m  − (n + 1)H]− (n = 1–4, m = 1–3). Regarding Cys, adduct clusters up to n = 5 and m = 4 were observed as well. Considering silver–GSH interactions, even doubly charged oligomers occur generating [Ag(a + 1)GSH a  − (a + 3)H]2− (a = 5–7) and [Ag b GSH b  − (b + 2)H]2− (b = 4–8) ions. 1H NMR data of free GSH compared to that after treatment with Ag+ confirm sulfur–metal interactions due to changing chemical shifts for the protons located adjacent to the thiol group. Density functional theory calculations for silver–GSH clusters may explain the formation of experimentally recorded large clusters due to cooperative effects between silver and carboxylic acid side chains. Both sets of experiments indicate the presence of these adducts in the liquid phase. For silver nanoparticles, the respective data confirm the release of silver ions and the subsequent adduct formation.

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Acknowledgments

F. Blaske would like to thank The German Federal Environmental Foundation (Deutsche Bundesstiftung Umwelt, DBU, Osnabrück, Germany) for financial support in form of a Ph.D. scholarship.

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Authors and Affiliations

  1. Institute of Inorganic and Analytical Chemistry, University of Münster, Corrensstraße 30, 48149, Münster, Germany

    Franziska Blaske, Lisa Stork, Michael Sperling & Uwe Karst

  2. European Virtual Institute for Speciation Analysis (EVISA), Mendelstraße 11, 48149, Münster, Germany

    Michael Sperling

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  1. Franziska Blaske
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  2. Lisa Stork
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  3. Michael Sperling
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  4. Uwe Karst
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Correspondence to Uwe Karst.

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Blaske, F., Stork, L., Sperling, M. et al. Adduct formation of ionic and nanoparticular silver with amino acids and glutathione. J Nanopart Res 15, 1928 (2013). https://doi.org/10.1007/s11051-013-1928-3

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