Development and characterization of pH-responsive nanocarriers for chemo-photothermal combination therapy of acidic tumors.

The combination of photothermal therapy and chemotherapy has been considered a promising strategy for improving the excellent antitumor activities of these treatments. In this study, we developed a new simple type of pH-sensitive chemo-photothermal combination agent capable of repeated exposures to a near-infrared (NIR) laser and evaluated its anticancer efficacy in vitro and in vivo. Doxorubicin (Dox) and gold nanoclusters (GNCs) were successfully co-loaded into pH-sensitive nanoparticles (poly(ethylene glycol)-poly[(benzyl-l-aspartate)-co-(N-(3-aminopropyl)imidazole-L-aspartamide)] (PEG-PABI)), resulting in a particle size of approximately120 nm with a narrow size distribution. The dual drug-loaded nanoparticles (Dox/GNC-loaded PEG-PABI micelles (Dox/GNC-Ms)) showed consistent pH-sensitive properties and heat generation efficiency after repeated NIR laser exposure. In particular, GNC-M has improved photothermal stability while maintaining high photothermal conversion efficiency, addressing the shortcomings of previous gold nanoparticles. As the concentration of GNC-Ms, irradiation light exposure time, and light source intensity increased, the amount of heat generated and the anticancer effect increased. When Dox was encapsulated with GNCs (Dox/GNC-Ms), a faster drug release rate under acidic pH conditions and a strong synergistic effect against U87MG cells were observed. When the Dox/GNC-M system was extended to in vivo studies, it effectively increased the temperature of the tumor tissue under near-infrared irradiation and showed excellent anticancer efficacy. Therefore, the Dox/GNC-M system could be a simple but promising strategy for chemo-photothermal combination treatment capable of targeting acidic tumors.

A novel gold nanocluster-based fluorometric biosensor for measuring prooxidant activity with a large Stokes shift.

A chicken egg white protein-protected gold nanocluster (CEW-AuNC) based fluorogenic biosensor, where protein was used as both reducing and protecting agent, was developed to determine the Cu(II)-induced prooxidant activity of natural antioxidants abundant in food and biological samples. Gold nanoclusters, prepared using egg white proteins, exhibited strong fluorescence. The prooxidant activity of the tested antioxidants was indirectly measured by their reducing action on Cu(II) to Cu(I), and the reduced cuprous ion was bound to the thiol groups in the CEW-AuNC structure, causing a decrease in fluorescence intensity. Epicatechin, catechin, epigallocatechin gallate, morin, rutin, quercetin, gallic, chlorogenic, and rosmarinic acids, glutathione, cysteine, N-acetyl cysteine, bilirubin, resveratrol, and α-tocopherol were studied as natural antioxidants. A fluorometric method showing a large Stokes shift with excitation/emission maxima at 360∕640 nm was developed to sensitively measure the decrease in the fluorescence of CEW-AuNC associated with the binding of copper(I) to the protein structure. Total prooxidant activities of the binary, ternary, and quaternary synthetic mixtures and of some food and synthetic serum samples were determined. The biosensor response was statistically compared to that of its spectrophotometric counterpart. This method can be used for the control of the oxidative stability of foods with a prolonged shelf life.

Unconventional application of gold nanoclusters/Zn-MOF composite for fluorescence turn-on sensitive detection of zinc ion.

Contrary to organic solvent-induced aggregation of Au nanoclusters (AuNCs), herein, we reported aggregation induced emission enhancement (AIEE) of AuNCs in an aqueous media through confinement of AuNCs by in situ formed Zn-MOF for detecting Zn2+. Glutathione capped AuNCs (GSH-AuNCs) was synthesized through reduction of Au3+ by glutathione. Zn2+ could significantly enhance the fluorescence of GSH-AuNCs upon addition of 2-methylimidazole, which was attributed to the formation of Zn-MOF. XRD and TEM were used to characterize the in situ formed Zn-MOF. Zn2+ induced aggregation was demonstrated by dynamic light scattering and TEM. The quantum yields (QYs) of AuNCs after aggregation induced by in situ formed Zn-MOF attained to 36.6%, which was nearly 9 times that of the sole AuNCs. On this basis, a fluorogenic sensor was reported for Zn2+ detection with a linear range from 12.3 nM to 24.6 µM and a detection limit of 6 nM (S/N = 3). The proposed sensor was successfully applied to assay the content of zinc in human serum, milk, water, and zinc sulfate syrup oral solution samples. The novel strategy proposed in this work may open a new window of interest in an unconventional application of gold nanoclusters/MOF nanoscale platform for metal ion detection and nutritional assessment of food.