Structure of a Thiol Monolayer-Protected Gold Nanoparticle at 1.1 Å Resolution

@article{Jadzinsky2007StructureOA,
  title={Structure of a Thiol Monolayer-Protected Gold Nanoparticle at 1.1 Å Resolution},
  author={Pablo D Jadzinsky and Guillermo Calero and Christopher J. Ackerson and David A. Bushnell and Roger D. Kornberg},
  journal={Science},
  year={2007},
  volume={318},
  pages={430 - 433}
}
Structural information on nanometer-sized gold particles has been limited, due in part to the problem of preparing homogeneous material. Here we report the crystallization and x-ray structure determination of a p-mercaptobenzoic acid (p-MBA)–protected gold nanoparticle, which comprises 102 gold atoms and 44 p-MBAs. The central gold atoms are packed in a Marks decahedron, surrounded by additional layers of gold atoms in unanticipated geometries. The p-MBAs interact not only with the gold but… 
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References

SHOWING 1-10 OF 38 REFERENCES

Divide and protect: capping gold nanoclusters with molecular gold-thiolate rings.

The calculated optical spectrum of this species features a large optical gap and a prominently peaked structure, correlating with experimental findings of "molecular-like spectra" of thiolate-protected 1.1 nm gold nanoparticles.

Chirality in bare and passivated gold nanoclusters

Detailed knowledge of the lattice structure, shape, morphology, surface structure, and bonding of bare and passivated gold clusters is fundamental to predict and understand their electronic, optical,…

Controlled Etching of Au:SR Cluster Compounds

When Au:SR cluster compounds (R = (CH2)5CH3) with an Au metallic cluster core mass of ∼14 kDa (∼75 atoms, 1.1 nm equivalent diameter), are heated in neat dodecane−thiol solution under inert…

Alkanethiolate Gold Cluster Molecules with Core Diameters from 1.5 to 5.2 nm: Core and Monolayer Properties as a Function of Core Size

The mean size of the gold (Au) core in the synthesis of dodecanethiolate-stabilized Au cluster compounds can be finely adjusted by choice of the Au:dodecanethiolate ratio and the temperature and rate…

Molecular Orientation and Ordered Structure of Benzenethiol Adsorbed on Gold(111)

The adsorption of benzenethiol on Au(111) from aqueous solution has been investigated by using surface-enhanced infrared absorption spectroscopy (SEIRAS), scanning tunneling microscopy (STM), and…

Isolation and Selected Properties of a 10.4 kDa Gold:Glutathione Cluster Compound

An unprecedented small thioaurite cluster compound (with metallic Au0 core) has been isolated in high yield by decomposition of polymeric Au(I)SG compounds, where GSH is the ubiquitous tripeptide…

Giant Gold−Glutathione Cluster Compounds: Intense Optical Activity in Metal-Based Transitions

A series of giant metal-cluster compounds, each composed of a gold core and a glutathione (GSH) adsorbate layer, have been prepared from Au(I)SG polymers and separated by gel electrophoresis, using…

Structural evolution of smaller gold nanocrystals: The truncated decahedral motif

It is commonly expected, and often observed, that the structures (and properties) of finite-size materials aggregates (clusters) differ from those of the bulk. However, determination of specific…

Formation and Structure of Self-Assembled Monolayers.

Monolayers of alkanethiolates on gold are probably the most studied SAMs to date and offer the needed design flexibility, both at the individual molecular and at the material levels, and offer a vehicle for investigation of specific interactions at interfaces, and of the effect of increasing molecular complexity on the structure and stability of two-dimensional assemblies.

Self-assembled monolayers of alkanethiols on Au(111): surface structures, defects and dynamics.

The surface structures, defects and dynamics of self-assembled monolayers (SAMs) on Au(111) are reviewed and the study of surface dynamics sheds light on the relative stability of some of these surface structures.