New research from Queen’s Carbon to Metal Coating Institute could lead to the use of tiny structures of gold to deliver precise cancer treatment.

The use of gold nanoclusters in biomedical applications has been steadily increasing in recent years. However, water solubility is a key factor for these applications, and water-soluble gold nanoclusters are often difficult to isolate and susceptible to exchange or oxidation in vivo. Herein, we report the isolation of N-heterocyclic carbene (NHC)-protected atomically precise gold nanoclusters functionalized with triethylene glycol monomethyl ether groups. These clusters are highly luminescent and water soluble and are shown to be stable in biological media. Importantly, the core structure, stability, and high quantum yield of the nanoclusters were conserved after backbone modification. Depending on the nature of the halide group, clusters have high stability in simulated biofluids and resist attack by glutathione. In vivo studies show that no abnormal cellular morphology is introduced in the kidney, liver, or spleen of mice treated with [Au13(NHC)5Br2]Br3 nanoclusters protected by 1,8-dimethylnaphthyl-linked NHCs. This cluster has a blood elimination half-life of 0.68 h. Functionalization of the wingtip groups of the cluster with azide groups is demonstrated, and complete reaction of all 10 azide groups with strained alkynes is shown, highlighting the potential of these clusters in biological settings.

N-heterocyclic carbene (NHC)-protected gold nanoclusters display high stability and high photoluminescence, making them well-suited for fluorescence imaging and photodynamic therapeutic applications. We report herein the synthesis of two bisNHC-protected Au13 nanoclusters with π-extended aromatic systems. Depending on the position of the π-extended aromatic system, changes to the structure of the ligand shell in the cluster are observed, with the ability to correlate increases in rigidity with increases in fluorescence quantum yield. Density functional theory analysis reveals that both synthesized Au13 nanoclusters are 8-electron superatoms but have distinct differences in the characteristics of the lowest unoccupied single-electron states. Qualitatively, this implies different mechanisms for excitations and their decay over the fundamental energy gap. Stability and photophysical studies were carried out to provide the emission lifetime and optical purity of the two clusters. Active intracellular uptake of the nanoclusters was confirmed in vitro using confocal microscopy in human epithelial carcinoma cells. Reactive oxygen species production was measured at 7% efficiency. The high cluster stability, photoluminescence quantum yields, and efficient cellular uptake in cancer cells suggest potential for these nanoclusters as highly efficient and tunable nanomedical platforms.