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@ARTICLE{Wetzel:893912,
      author       = {Wetzel, Oliver and Hosseini, Shabnam and Loza, Kateryna and
                      Heggen, Marc and Prymak, Oleg and Bayer, Peter and Beuck,
                      Christine and Schaller, Torsten and Niemeyer, Felix and
                      Weidenthaler, Claudia and Epple, Matthias},
      title        = {{M}etal–{L}igand {I}nterface and {I}nternal {S}tructure
                      of {U}ltrasmall {S}ilver {N}anoparticles (2 nm)},
      journal      = {The journal of physical chemistry / B},
      volume       = {125},
      number       = {21},
      issn         = {1520-5207},
      address      = {Washington, DC},
      publisher    = {Soc.},
      reportid     = {FZJ-2021-02924},
      pages        = {5645 - 5659},
      year         = {2021},
      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 situ1H 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.},
      cin          = {ER-C-1},
      ddc          = {530},
      cid          = {I:(DE-Juel1)ER-C-1-20170209},
      pnm          = {5351 - Platform for Correlative, In Situ and Operando
                      Characterization (POF4-535)},
      pid          = {G:(DE-HGF)POF4-5351},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {34029093},
      UT           = {WOS:000661116600019},
      doi          = {10.1021/acs.jpcb.1c02512},
      url          = {https://juser.fz-juelich.de/record/893912},
}