Journal Article FZJ-2021-02924

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

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2021
Soc. Washington, DC

The journal of physical chemistry <Washington, DC> / B 125(21), 5645 - 5659 () [10.1021/acs.jpcb.1c02512]

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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 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.

Classification:

Contributing Institute(s):
  1. Physik Nanoskaliger Systeme (ER-C-1)
Research Program(s):
  1. 5351 - Platform for Correlative, In Situ and Operando Characterization (POF4-535) (POF4-535)

Appears in the scientific report 2021
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Medline ; Embargoed OpenAccess ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; Essential Science Indicators ; IF < 5 ; JCR ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection
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 Record created 2021-07-07, last modified 2021-08-10


Published on 2021-05-24. Available in OpenAccess from 2022-05-24.:
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