Solid-state thiolate-stabilized copper nanoclusters with ultrahigh photoluminescence quantum yield for white light-emitting devices.

As a new emerging candidate for solid-state phosphors, copper nanoclusters (CuNCs) have gained tremendous interest in the field of white light-emitting devices (WLEDs). However, their further applications are impeded by the low photoluminescence quantum yield (PLQY) and poor emission color tunability of CuNCs. This work demonstrates the synthesis of cyan and orange emitting CuNCs, and their combination as color conversion phosphors in WLEDs. The cyan and orange emitting CuNCs were prepared employing 2-mercapto-1-methylimidazole (MMI) and N-acetyl-l-cysteine (NAC), respectively, as stabilizing-cum-reducing agents. The dispersions of MMI-CuNCs and NAC-CuNCs are weakly emissive. However, after processing into powders, they both possess ultrahigh PLQYs (45.2% for MMI-CuNCs, and 64.6% for NAC-CuNCs) owing to the effect of aggregation-induced emission (AIE). All-CuNC based WLEDs are then designed and developed using powdered MMI-CuNC and NAC-CuNC samples on commercially available 365 nm GaN LED chips. They display acceptable white light characteristics with a Commission Internationale de l'Eclairage coordinate value and color rendering index of (0.26, 0.30) and 83, respectively. We believe that these cost-effective and eco-friendly CuNCs with interesting AIE properties will vigorously promote the development of high-quality WLEDs for commercial applications.

Protein-Supported RuO2 Nanoparticles with Improved Catalytic Activity, In Vitro Salt Resistance, and Biocompatibility: Colorimetric and Electrochemical Biosensing of Cellular H2O2.

Protein-supported nanoparticles have a great significance in scientific and nanotechnology research because of their "green" process, low cost-in-use, good biocompatibility, and some interesting properties. Ruthenium oxide nanoparticles (RuO2NPs) have been considered to be an important member in nanotechnology research. However, the biosynthetic approach of RuO2NPs is relatively few compared to those of other nanoparticles. To address this challenge, this work presented a new way for RuO2NP synthesis (BSA-RuO2NPs) supported by bovine serum albumin (BSA). BSA-RuO2NPs are confirmed to exert peroxidase-like activity, electrocatalytic activity, in vitro salt resistance (2 M NaCl), and biocompatibility. Results indicate that BSA-RuO2NPs have higher affinity binding for 3,3',5,5'-tetramethylbenzidine or H2O2 than bare RuO2NPs. Moreover, BSA turns out to be a crucial factor in promoting the stability of RuO2NPs. Taking the advantages of these improved properties, we established colorimetric (linear range from 2 to 800 µM, a limit of detection of 1.8 µM) and electrochemical (linear range from 0.4 to 3850 µM, a limit of detection of 0.18 µM) biosensors for monitoring in situ H2O2 secretion from living MCF-7 cells. Herein, this work offers a new biosynthesis strategy to obtain BSA-RuO2NPs and sheds light on the sensitive biosensors to monitor the H2O2 secreted from living cells for promising applications in the fields of nanotechnology, biology, biosensors, and medicine.

Fluorescent gold nanocluster-based sensor for detection of alkaline phosphatase in human osteosarcoma cells.

Gold nanoclusters (AuNCs) have attracted much attention as signal transducers in photoluminescence chemical/biological sensors. Herein, we employ bovine serum albumin/3-mercaptopropionic acid co-modified AuNCs as a fluorescence probe, Fe3+ as a quencher, and pyrophosphate as an alkaline phosphatase (ALP) substrate and Fe3+ chelator to design a novel biosensor for ALP detection, achieving a detection linear range of 0.8-16 U/L and a detection limit of 0.78 U/L. The developed method is successfully applied to the detection of ALP in human osteosarcoma cells and is shown to be suited for ALP inhibitor screening.

Preparation of strongly fluorescent water-soluble dithiothreitol modified gold nanoclusters coated with carboxychitosan, and their application to fluorometric determination of the immunosuppressive 6-mercaptopurine.

Water-soluble and non-aggregating gold nanoclusters (AuNCs) were obtained by modification of the AuNCs with dithiothreitol (DTT) and then coating them with carboxylated chitosan. This process remarkably enhances the dispersibility of DTT-coated AuNCs in water. The resulting AuNCs, on photoexcitation at 285 nm, display strong red emission with a maximum at 650 nm and a 23% quantum yield. Fluorescence is strongly and selectively suppressed in the presence of 6-mercaptopurine (6-MP). Photoluminescence drops linearly in the 0.1-100 µM 6-MP concentration range, and the detection limit of this assay is 0.1 µM. Other features of the modified AuNCs include a decay time of 8.56 µs, a 365 nm Stokes shift, good colloidal stability, ease of chemical modification, and low toxicity. Conceivably, these NCs may find a range of applications in biological imaging and optical sensing. Graphical abstract Highly fluorescent and water-soluble gold nanoclusters (AuNCs) were obtained by modification of the AuNCs with dithiothreitol (DTT) and then coating them with carboxylated chitosan (CC). The resulting CC/DTT-AuNCs were used for sensitive and selective detection of 6-mercaptopurine.

An ammonia-based etchant for attaining copper nanoclusters with green fluorescence emission.

Luminescent copper nanoclusters (CuNCs) constitute a very active research topic due to their unique properties and lower cost than gold and silver NCs. In this study, we report a new, facile, and rapid top-down etching method for synthesizing luminescent CuNCs, using Cu nanoparticles (CuNPs) as the precursor and ammonia (NH3) as the etchant. The etching mechanism is systematically investigated and the optical and structural properties of the obtained CuNCs are carefully studied. The NH3-triggered etching process is very fast and the newly generated CuNCs can emit strong green fluorescence with a high quantum yield. Moreover, by coupling the urease-catalyzed hydrolysis of urea with the NH3-induced etching of CuNPs, we developed a novel fluorescence turn-on assay for urea. The linear range for urea detection is from 0.25 to 5 mM, and the limit of detection is 0.01 mM. This novel sensing approach, with good sensitivity and excellent selectivity, is then successfully utilized to detect urea in human serum samples, demonstrating its great potential in clinical diagnosis. In addition, the proposed coupling method can be extended to monitor other analytes that influence the size-focusing etching process, allowing metal NCs to be used to construct diverse chemosensors and biosensors.

Chitosan-stabilized platinum nanoparticles as effective oxidase mimics for colorimetric detection of acid phosphatase.

Capping molecules on the surface of nanomaterials not only enhance the dispersion and stability of nanomaterials but also greatly facilitate their surface modification and biological applications. However, most capping molecules can severely block the active sites of the catalytic core, thereby decreasing the enzymatic activity of nanomaterial-based enzyme mimics. This work demonstrates the superiority of chitosan (Ch) as a capping molecule for synthesizing catalytic platinum nanoparticles (PtNPs). The experimental results show that Ch simultaneously exhibits an excellent stabilizing effect and enhances the oxidase-like activity of PtNPs. Kinetic studies indicate that Ch-PtNPs have a higher affinity for 3,3',5,5'-tetramethylbenzidine (TMB) than other kinds of oxidase mimics. Furthermore, the TMB chromogenic reaction catalyzed by Ch-PtNPs is found to be much faster in an acidic medium, thus adapting well to the optimal pH for acid phosphatase (ACP). Therefore, a novel colorimetric approach for ACP determination is developed for the first time, which is based on the Ch-PtNP-catalyzed oxidation of TMB, the inhibitory effect of ascorbic acid (AA) on the oxidase-like activity of Ch-PtNPs, and the ACP-catalyzed hydrolysis of AA 2-phosphate (AAP) into AA. The linear range for ACP is 0.25-2.5 U L-1 and the limit of detection is measured to be 0.016 U L-1. This new colorimetric method is utilized to detect ACP in real biological samples and to screen ACP inhibitors. We believe that these new PtNPs, which exhibit high colloidal stability, excellent catalytic performance, good biocompatibility, simple preparation, and easy modification, can be promising candidates for a broad range of applications in optical sensing, environmental monitoring, clinical diagnosis, and drug discovery.