pH-Responsive Near-Infrared Emitting Gold Nanoclusters.

Near-infrared (NIR) fluorophores with pH-responsive properties suggest merits in biological analyses. This work establishes a general and effective method to obtain pH-responsive NIR emissive gold nanoclusters by introducing aliphatic tertiary amine (TA) groups into the ligands. Computational study suggests that the pH-responsive NIR emission is associated with electronic structure change upon protonation and deprotonation of TA groups. Photo-induced electron transfer between deprotonated TA groups and the surface Au-S motifs of gold nanoclusters can disrupt the radiative transitions and thereby decrease the photoluminescence intensity in basic environments (pH=7-11). By contrast, protonated TA groups curb the electron transfer and restore the photoluminescence intensity in acidic environments (pH=4-7). The pH-responsive NIR-emitting gold nanoclusters serve as a specific and sensitive probe for the lysosomes in the cells, offering non-invasive emissions without interferences from intracellular autofluorescence.

Design of Fluoro-Free Surfaces Super-Repellent to Low-Surface-Tension Liquids.

Super-liquid-repellent surfaces feature high liquid contact angles and low sliding angles find key applications in anti-fouling and self-cleaning. While repellency for water is easily achieved with hydrocarbon functionalities, repellency for many low-surface-tension liquids (down to 30 mN m-1 ) still requires perfluoroalkyls (a persistent environmental pollutant and bioaccumulation hazard). Here, the scalable room-temperature synthesis of stochastic nanoparticle surfaces with fluoro-free moieties is investigated. Silicone (dimethyl and monomethyl) and hydrocarbon surface chemistries are benchmarked against perfluoroalkyls, assessed using model low-surface-tension liquids (ethanol-water mixtures). It is discovered that both hydrocarbon- and dimethyl-silicone-based functionalization can achieve super-liquid-repellency down to 40-41 mN m-1 and 32-33 mN m-1 , respectively (vs 27-32 mN m-1 for perfluoroalkyls). The dimethyl silicone variant demonstrates superior fluoro-free liquid repellency likely due to its denser dimethyl molecular configuration. It is shown that perfluoroalkyls are not necessary for many real-world scenarios requiring super-liquid-repellency. Effective super-repellency of different surface chemistries against different liquids can be adequately predicted using empirically verified phase diagrams. These findings encourage a liquid-centric design, i.e., tailoring surfaces for target liquid properties. Herein, key guidelines are provided for achieving functional yet sustainably designed super-liquid-repellency.

Bright and Photostable Fluorescent Metal Nanocluster Supraparticles from Invert Emulsions.

Fluorescent supraparticles of gold, silver and copper nanoclusters are synthesized by simply drying of invert emulsions, resulting in a dozen-fold increase in photoluminescence quantum yield (up to ≈80 %) and a significant improvement in photostability. The inhibition of the ligand twisting during the intramolecular charge transfer is found to be responsible for the enhancement, especially for the gold nanocluster supraparticles. This research provides a general, flexible, and easy method for producing highly luminescent and photostable metal nanocluster-based materials that promise practical applications in white-light-emitting diodes.

Fluorescent Au nanoclusters stabilized by silane: facile synthesis, color-tunability and photocatalytic properties.

Synthesis of tunable, luminescent metal nanoclusters remains challenging due to their tendency to aggregate. Herein, we report a simple photoreduction method to synthesize fluorescent silane-stabilized Au nanoclusters. By altering the molar ratio of stabilizer and Au precursor, emissions of the as-prepared Au nanoclusters can be tuned in the wavelength range of 538-580 nm. High resolution transmission electron microscopy results showed that the variation in the size of the as-formed nanoclusters (1.2-2.0 nm) might be responsible for this emission shift. The as-synthesized gold nanoclusters have a relatively long fluorescence lifetime, from 34.04 to 46.83 ns, and luminescence quantum yields of 0.26-3.16%, depending on the fluorescence at the specific emission wavelength. Compared with bulk gold, these silane-stabilized Au nanoclusters possess special electronic structures and exhibit semiconductor-like features such as an absorption edge in the visible region, which gives rise to their visible excitation at 400-450 nm. As demonstrated by the degradation of methylene blue under visible irradiation, the synthesized Au nanoclusters can also function as a promising cluster photocatalyst, just like many other semiconductor counterparts.