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  Metal–Ligand Interface and Internal Structure of Ultrasmall Silver Nanoparticles (2 nm)

Wetzel, O., Hosseini, S., Loza, K., Heggen, M., Prymak, O., Bayer, P., et al. (2021). Metal–Ligand Interface and Internal Structure of Ultrasmall Silver Nanoparticles (2 nm). The Journal of Physical Chemistry B, 125(21), 5645-5659. doi:10.1021/acs.jpcb.1c02512.

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 Creators:
Wetzel, Oliver1, Author
Hosseini, Shabnam1, Author
Loza, Kateryna1, Author              
Heggen, Marc2, Author
Prymak, Oleg1, Author              
Bayer, Peter3, Author              
Beuck, Christine3, Author
Schaller, Torsten4, Author
Niemeyer, Felix4, Author
Weidenthaler, Claudia5, Author              
Epple, Matthias1, Author
Affiliations:
1Inorganic Chemistry and Center for Nanointegration Duisburg-Essen (CeNIDE), Universitaetsstr. 5-7, Essen, Germany, ou_persistent22              
2Ernst Ruska-Centre for Microscopy and Spectroscopy with Electrons, Forschungszentrum Jülich GmbH, 52425 Jülich, Germany, ou_persistent22              
3Department of Structural and Medicinal Biochemistry, Centre for Medical Biotechnology (ZMB), University of Duisburg-Essen, 45117 Essen, Germany, ou_persistent22              
4Organic Chemistry, University of Duisburg-Essen, Universitaetsstrasse 5-7, 45117 Essen, Germany, ou_persistent22              
5Research Group Weidenthaler, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1950291              

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 Abstract: Ultrasmall silver nanoparticles were prepared by reduction with NaBH4 and surface-terminated with glutathione (GSH). The particles had a solid core diameter of 2 nm as shown by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). NMR-DOSY gave a hydrodynamic diameter of 2 to 2.8 nm. X-ray photoelectron spectroscopy (XPS) showed that silver is bound to the thiol group of the central cysteine in glutathione under partial oxidation to silver(+I). In turn, the thiol group is deprotonated to thiolate. X-ray powder diffraction (XRD) together with Rietveld refinement confirmed a twinned (polycrystalline) fcc structure of ultrasmall silver nanoparticles with a lattice compression of about 0.9% compared to bulk silver metal. By NMR spectroscopy, the interaction between the glutathione ligand and the silver surface was analyzed, also with 13C-labeled glutathione. The adsorbed glutathione is fully intact and binds to the silver surface via cysteine. In situ 1H NMR spectroscopy up to 85 °C in dispersion showed that the glutathione ligand did not detach from the surface of the silver nanoparticle, i.e. the silver–sulfur bond is remarkably strong. The ultrasmall nanoparticles had a higher cytotoxicity than bigger particles in in vitro cell culture with HeLa cells with a cytotoxic concentration of about 1 μg mL–1 after 24 h incubation. The overall stoichiometry of the nanoparticles was about Ag∼250GSH∼155.

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Language(s): eng - English
 Dates: 2021-03-192021-05-162021-05-242021-06-03
 Publication Status: Published in print
 Pages: 15
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.jpcb.1c02512
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Title: The Journal of Physical Chemistry B
  Abbreviation : J. Phys. Chem. B
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 125 (21) Sequence Number: - Start / End Page: 5645 - 5659 Identifier: ISSN: 1520-6106
CoNE: https://pure.mpg.de/cone/journals/resource/1000000000293370_1