Structure of the thiolated Au130 cluster.

The structure of the recently discovered Au130-thiolate and -dithiolate clusters is explored in a combined experiment-theory approach. Rapid electron diffraction in scanning/transmission electron microscopy (STEM) enables atomic-resolution imaging of the gold core and the comparison with density functional theory (DFT)-optimized realistic structure models. The results are consistent with a 105-atom truncated-decahedral core protected by 25 short staple motifs, incorporating disulfide bridges linking the dithiolate ligands. The optimized structure also accounts, via time-dependent DFT (TD-DFT) simulation, for the distinctive optical absorption spectrum, and rationalizes the special stability underlying the selective formation of the Au130 cluster in high yield. The structure is distinct from, yet shares some features with, each of the known Au102 and Au144/Au146 systems.

Enhancing near IR luminescence of thiolate Au nanoclusters by thermo treatments and heterogeneous subcellular distributions.

A five-to-ten fold enhancement, up to ca. 5-10% quantum efficiency, of near IR luminescence from monothiolate protected gold nanoclusters was achieved by heating in the presence of excess ligand thiols. An emission maximum in the 700-900 nm range makes these Au nanoclusters superior for bioimaging applications over other emissions centered below 650 nm due to reduced background interference, albeit visible emissions could have higher quantum efficiency. The heating procedure is shown to be effective to improve the luminescence of Au nanoclusters synthesized under a variety of conditions using two types of monothiols: mercaptosuccinic acid and tiopronin. Therefore, this heating method is believed to be a generalizable approach to improve the near IR luminescence of aqueous soluble Au nanoclusters, which enables better bioimaging applications. The high quantum yield is found relatively stable over a wide pH range. PEGylation of the Au nanoclusters reduces their quantum efficiency but improves their permeation into the cytoplasm. Interestingly, z-stack confocal analysis clearly reveals the presence of Au nanoclusters inside the cell nucleus in single cell imaging. The finding addresses controversial literature reports and demonstrates the internalization and heterogeneous subcellular distributions, particularly inside the nucleus. The high luminescence intensity, small overall dimension, cell and nuclear distribution, chemical stability and low-to-non toxicity make these Au nanoclusters promising probes for broad cell dynamics and imaging applications.

Fluorescence Intensity and Lifetime Cell Imaging with Luminescent Gold Nanoclusters.

In this article, luminescent properties of gold nanoclusters (AuNCs) were studied at the single nanoparticle level and also used as novel imaging agents in cell media. Two types of water-soluble AuNCs which were stabilized with a monolayer composed of either mercaptosuccinic acid (MSA) or tiopronin thiolate ligands were synthesized by a chemical reduction reaction. These AuNCs were determined to have an average core diameter of less than 2 nm. On a time-resolved confocal microscope, the emission signals from the single AuNCs were distinctly recordable. The quantum yields of these AuNCs were measured to be ca. 5%. The lifetime of these AuNCs is also much longer than the lifetime of cellular autofluorescence in lifetime cell imaging as well as the lifetime of organic dye Alexa Fluor 488. After being derivatized with polyethylene glycol (PEG) moieties, the AuNCs were uploaded efficiently in the HeLa cells. Fluorescence intensity and lifetime cell images were recorded on the time-resolved confocal microscope in which the emission from the AuNCs was readily differentiated from the cellular autofluorescence background because of their relatively stronger emission intensities and longer lifetimes. These loaded nanoclusters in the cells were observed to widely distribute throughout the cells and especially densely loaded near the cell nucleuses. The AuNCs in the cells were also tested to have a better photostability relative to the organic fluorophores under the same conditions. We thus conclude that the AuNCs have a great potential as novel nanoparticle imaging agents, especially as lifetime imaging agents, in fluorescence imaging applications. We also prospect much broader applications of these AuNCs after further improvements of their luminescence quantum yields.