This paper presents a one-pot approach for preparing highly fluorescent Au(8) clusters by reacting the Au(3+) precursor solution with lysozyme type VI (Lys VI) at pH 3. The fluorescence band of (Lys VI)-stabilized Au(8) clusters is centered at 455 nm on the excitation at 380 nm. Blue-emitting Au(8) clusters have a high quantum yield (∼56%), two fluorescence lifetimes, and a rare amount of Au(+) on the surface of the Au core. When the pH of a solution of Au(8) clusters increases suddenly to 12, the Au(8) clusters gradually convert to Au(25) clusters over time. This conversion is also observed in the case of (Lys VI)-directed synthesis of Au(25) clusters at pH 12. The pH-induced conversion of Au(8) to Au(25) clusters suggests that the size of (Lys VI)-stabilized gold nanoclusters (AuNCs) relies on the secondary structure of Lys VI, which is susceptible to pH change. Based on these results and previous literature, this paper proposes the possible mechanism for growing (Lys VI)-stabilized Au(8) and Au(25) clusters. Additionally, (Lys VI)-stabilized Au(8) clusters could sense glutathione (GSH) through GSH-induced core-etching of Au(8) clusters; the limit of detection at a signal-to-noise ratio of 3 for GSH is determined to be 20 nm. Except for cysteine, the selectivity of (Lys VI)-stabilized Au(8) clusters for GSH over amino acids is remarkably high. The practicality of using Au(8) clusters to determine the concentration of GSH in a single drop of blood is also validated.

We present a simple, one-pot approach for synthesizing ultrafine platinum (Pt) nanoclusters (NCs) under alkaline conditions using lysozyme (Lys) as a template. From the analysis of the nanoclusters by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, Lys VI-stabilized Pt NCs majorly consisted of Pt4 clusters. The formation of Pt NCs was confirmed using X-ray photoelectron spectroscopy and Fourier-transformed infrared spectroscopy. The maximal fluorescence of Pt NCs appears at 434 nm with a quantum yield of 0.08, a fluorescence lifetime of 3.0 ns, and excitation-dependent emission wavelength behavior. Pt NCs exhibit an intrinsic oxidase-like activity because Pt NCs can catalyze O2 oxidation of organic substrates through a four-electron reduction process. Compared with larger Pt nanoparticles, the Pt NCs produce substantially greater catalytic activity in the O2-mediated oxidation of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid), 3,3',5,5'-tetramethylbenzidine, and dopamine.

In this work, we report a highly sensitive colorimetric sensing strategy for cancer biomarker diagnosis using gold nanoparticles (AuNPs) labeled with biotinylated poly(adenine) ssDNA sequences and streptavidin-horseradish peroxidase for enzymatic signal enhancement. By adopting this DNA-AuNP nanoconjugate sensing strategy, we were able to eliminate the complicated and costly thiol-binding process typically used to modify AuNP surfaces with ssDNA. In addition, different antibodies can be introduced to the AuNP surfaced via electrostatic interactions to provide highly specific recognition sites for biomolecular sensing. Moreover, multiple, simultaneous tests can be rapidly performed with low sample consumption by incorporating these surface-modified AuNPs into a paper-based analytical device that can be read using just a smartphone. As a result of these innovations, we were able to achieve a detection limit of 10 pg/mL for a prostate specific antigen in a test that could be completed in as little as 15 min. These results suggest that the proposed paper platform possesses the capability for sensitive, high-throughput, and on-site prognosis in resource-limited settings.

This study describes a bottom-up assembly route for monodisperse carbon dots (CDs) into different sizes of CD aggregates through the control of the concentration of fatty acids. The highly monodisperse CDs were prepared via solvent-thermal treatment of edible soybean oil, which generated glycerol-based polymer as a carbon source and fatty acid as a surface capping in the synthetic process. The as-synthesized CDs exhibited small particle size variation (2.7 ± 0.2 nm) and narrow emission bands (full width at half-maximum <20 nm). The monodisperse CDs can self-assemble into blue-, green-, yellow-, and red-emitting CD aggregates by tuning the concentration of fatty acids. Compared to commercially available organic dyes and semiconductor quantum dots, the CD aggregates provided a 10-7000-fold improvement in brightness. Additionally, their emission wavelength was tunable across the entire visible spectrum by tuning the excitation wavelength. Because of their high brightness, fluorescence imaging of a single carbon dot and CD aggregate was simply achieved using filter-free dark-field fluorescence microscopy (DFM). We also demonstrate the use of filter-free DFM to dynamically image cellular uptake of the monodisperse CDs in MCF-7 cells and Huh-7 liver cancer cells. Without the conjugation of the fluorophore to the CDs, the particle aggregation-induced red-shifted emission enables the development of the CD-based ratiometric sensor for Fe ions and pyrophosphate based on Fe-induced aggregation of the monodisperse CDs.