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Structural patterns at all scales in a nonmetallic chiral Au133(SR)52 nanoparticle.

Zeng C, Chen Y, Kirschbaum K, Appavoo K, Sfeir MY, Jin R - Sci Adv (2015)

Bottom Line: These complex surface patterns have not been observed in the smaller nanoparticles.We further demonstrate that the Au133(SR)52 nanoparticle exhibits nonmetallic features in optical and electron dynamics measurements.Our work uncovers the elegant self-organization strategies in assembling a highly robust nanoparticle and provides a conceptual advance in scientific understanding of pattern structures.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA.

ABSTRACT
Structural ordering is widely present in molecules and materials. However, the organization of molecules on the curved surface of nanoparticles is still the least understood owing to the major limitations of the current surface characterization tools. By the merits of x-ray crystallography, we reveal the structural ordering at all scales in a super robust 133-gold atom nanoparticle protected by 52 thiolate ligands, which is manifested in self-assembled hierarchical patterns starting from the metal core to the interfacial -S-Au-S- ladder-like helical "stripes" and further to the "swirls" of carbon tails. These complex surface patterns have not been observed in the smaller nanoparticles. We further demonstrate that the Au133(SR)52 nanoparticle exhibits nonmetallic features in optical and electron dynamics measurements. Our work uncovers the elegant self-organization strategies in assembling a highly robust nanoparticle and provides a conceptual advance in scientific understanding of pattern structures.

No MeSH data available.


Total structure of chiral Au133(SR)52 nanoparticle characterized by x-ray crystallography.(A) An enantiomer of the chiral Au133(SR)52 nanoparticle. Magenta: gold; yellow: sulfur; gray: carbon; white: hydrogen. (B) Ensemble packing of Au133(SR)52 nanoparticles in P space group. The left- and right-handed enantiomers are indicated in magenta and green.
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Figure 1: Total structure of chiral Au133(SR)52 nanoparticle characterized by x-ray crystallography.(A) An enantiomer of the chiral Au133(SR)52 nanoparticle. Magenta: gold; yellow: sulfur; gray: carbon; white: hydrogen. (B) Ensemble packing of Au133(SR)52 nanoparticles in P space group. The left- and right-handed enantiomers are indicated in magenta and green.

Mentions: The magic-sized Au133(SR)52 nanoparticle was obtained via a thermal reaction of molecularly pure Au144(SCH2CH2Ph)60 nanoparticles (26) with excess 4-tert-butylbenzenethiol at 80°C for 4 days (see Supplementary Materials for details). The Au133(SR)52 nanoparticles crystallized in space group P; the final anisotropic (Au and S atoms) refinement converged at R1 = 8.65% for the observed data (tables S2 to S4). Figure 1 shows the total structure of an enantiomer of the Au133(SR)52 nanoparticle and packing of the racemic pair in the crystal. The diameter of the entire nanoparticle (including the ligand shell) is ~3.0 nm, with the metal core diameter being ~1.7 nm. The Au133(SR)52 nanoparticle is charge-neutral, evidenced by electrospray ionization mass spectrometry analysis; thus, cesium acetate was added to form positively charged cesium adducts of the Au133(SR)52 nanoparticle (15). Two strong peaks at mass/charge ratio (m/z) = 17,528.3 and 11,729.9 are observed (fig. S1), corresponding to [Au133(SR)52 + 2Cs]2+ (expected m/z = 17,528.20, deviation: 0.1) and [Au133(SR)52 + 3Cs]3+ (expected m/z = 11,729.77, deviation: 0.13); that is, the nanoparticle’s intrinsic charge is zero.


Structural patterns at all scales in a nonmetallic chiral Au133(SR)52 nanoparticle.

Zeng C, Chen Y, Kirschbaum K, Appavoo K, Sfeir MY, Jin R - Sci Adv (2015)

Total structure of chiral Au133(SR)52 nanoparticle characterized by x-ray crystallography.(A) An enantiomer of the chiral Au133(SR)52 nanoparticle. Magenta: gold; yellow: sulfur; gray: carbon; white: hydrogen. (B) Ensemble packing of Au133(SR)52 nanoparticles in P space group. The left- and right-handed enantiomers are indicated in magenta and green.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4643822&req=5

Figure 1: Total structure of chiral Au133(SR)52 nanoparticle characterized by x-ray crystallography.(A) An enantiomer of the chiral Au133(SR)52 nanoparticle. Magenta: gold; yellow: sulfur; gray: carbon; white: hydrogen. (B) Ensemble packing of Au133(SR)52 nanoparticles in P space group. The left- and right-handed enantiomers are indicated in magenta and green.
Mentions: The magic-sized Au133(SR)52 nanoparticle was obtained via a thermal reaction of molecularly pure Au144(SCH2CH2Ph)60 nanoparticles (26) with excess 4-tert-butylbenzenethiol at 80°C for 4 days (see Supplementary Materials for details). The Au133(SR)52 nanoparticles crystallized in space group P; the final anisotropic (Au and S atoms) refinement converged at R1 = 8.65% for the observed data (tables S2 to S4). Figure 1 shows the total structure of an enantiomer of the Au133(SR)52 nanoparticle and packing of the racemic pair in the crystal. The diameter of the entire nanoparticle (including the ligand shell) is ~3.0 nm, with the metal core diameter being ~1.7 nm. The Au133(SR)52 nanoparticle is charge-neutral, evidenced by electrospray ionization mass spectrometry analysis; thus, cesium acetate was added to form positively charged cesium adducts of the Au133(SR)52 nanoparticle (15). Two strong peaks at mass/charge ratio (m/z) = 17,528.3 and 11,729.9 are observed (fig. S1), corresponding to [Au133(SR)52 + 2Cs]2+ (expected m/z = 17,528.20, deviation: 0.1) and [Au133(SR)52 + 3Cs]3+ (expected m/z = 11,729.77, deviation: 0.13); that is, the nanoparticle’s intrinsic charge is zero.

Bottom Line: These complex surface patterns have not been observed in the smaller nanoparticles.We further demonstrate that the Au133(SR)52 nanoparticle exhibits nonmetallic features in optical and electron dynamics measurements.Our work uncovers the elegant self-organization strategies in assembling a highly robust nanoparticle and provides a conceptual advance in scientific understanding of pattern structures.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA.

ABSTRACT
Structural ordering is widely present in molecules and materials. However, the organization of molecules on the curved surface of nanoparticles is still the least understood owing to the major limitations of the current surface characterization tools. By the merits of x-ray crystallography, we reveal the structural ordering at all scales in a super robust 133-gold atom nanoparticle protected by 52 thiolate ligands, which is manifested in self-assembled hierarchical patterns starting from the metal core to the interfacial -S-Au-S- ladder-like helical "stripes" and further to the "swirls" of carbon tails. These complex surface patterns have not been observed in the smaller nanoparticles. We further demonstrate that the Au133(SR)52 nanoparticle exhibits nonmetallic features in optical and electron dynamics measurements. Our work uncovers the elegant self-organization strategies in assembling a highly robust nanoparticle and provides a conceptual advance in scientific understanding of pattern structures.

No MeSH data available.