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Quantum dots (QDs) are significant fluorescent materials for energy transfer studies with phthalocyanines (Pcs) and phthalocyanine (Pc) like biomolecules (like chlorophylls). Especially, carbon based QDs are used in numerous studies concerning energy transfer studies with chlorophylls, but the number of studies concerning energy transfer between phthalocyanines and carbon based QDs are limited. In this study, peripherally, hydroxythioethyl terminal groups substituted metal-free (H2 Pc) and zinc phthalocyanine (ZnPc) were non-covalently (electrostatic and/or π-π interaction) attached to carbon QDs, containing boron and nitrogen to form QDs-Pc nanoconjugates. The QDs-Pc conjugates were characterized using different spectroscopic techniques (FT-IR, TEM). Absorption and fluorescence properties of QDs-Pc structures in solution were studied. It was found that the quantum yields of the QDs slightly decreased from 30 % to 25 % upon doping the QDs with heteroatoms, B and N. The FRET efficiency was calculated as 33 % for BCN-QD/ZnPc. For the other conjugates, almost no energy transfer from QDs to Pc cores was observed. It was shown that the energy transfer between QDs to Pc cores were completely different from the energy transfer between QDs and photosynthetic pigments, and concluded that heteroatom doping in QD structure and existence of zinc metal in phthalocyanine structure is obligatory for an efficient energy transfer.

Super‐resolution fluorescence imaging provides critically improved information about the composition, organization, and dynamics of subcellular structures. Quantum dot triexciton imaging (QDTI) has been introduced as an easy‐to‐use sub‐diffraction imaging method that achieves an almost 2‐fold improvement in resolution when used with conventional confocal microscopes. Here, we report an overall 3‐fold increase in lateral and axial resolution compared to conventional confocal microscopes by combining QDTI with state‐of‐the‐art commercial laser scanning microscope systems., We report an overall 3‐fold increase in lateral and axial image resolution for confocal fluorescence microscopy by combining quantum dot triexciton imaging with state‐of‐the‐art commercial laser scanning microscope systems. Based on quantum dots as fluorescent labels, we present an easy‐to‐use super‐resolution method. A single confocal scan with minimal image post‐processing is sufficient to produce a sub‐diffraction image with an image resolution of approx. 80 nm lateral and 200 nm axial.

Uranium is an important nuclear fuel and the risk of human exposure to uranium increases as increasing amounts of uranium-containing waste enter the environment due to the rapid growth of nuclear power. Therefore, rapid, sensitive, and portable uranium detection is a promising approach to effectively control and monitor uranium contamination. To achieve this goal, abundant oxygen- and nitrogen-containing groups were introduced to molybdenum oxide quantum dot (MoOx QDs) surfaces with dopamine (DA) modification. Due to the excellent coordination ability of oxygen- and nitrogen-containing groups with uranium, the obtained DA-functionalized MoOx QDs (DA-MoOx QDs) showed a strong binding affinity for uranium and sensitivity was increased nearly 1000-fold compared with MoOx QDs alone. The limit of detection was 3.85 nM, which is higher than most of the reported nanomaterials. Moreover, the DA-MoOx QD-based method showed high selectivity and uranium could be clearly detected under masking with ethylenediaminetetraacetic acid even when the concentration of other metal ions was 100-fold higher than that of uranium, showing a very promising method for uranium contamination control and monitoring.

This work focuses on the systematic investigation of the shape, size, and composition-controlled synthesis of perovskite nanocrystals (NCs) under inert gas-free conditions and using pre-synthesized precursor stock solutions. In the case of CsPbBr3 NCs, we find that the lowering of reaction temperature from ∼175 to 100 °C initially leads to a change of morphology from bulk-like 3D nanocubes to 0D nanocubes with 3D-quantum confinement, while at temperatures below 100 °C the reaction yields 2D nanoplatelets (NPls) with 1D-quantum confinement. However, to our surprise, at higher temperatures (∼215 °C), the reaction yields CsPbBr3 hexapod NCs, which have been rarely reported. The synthesis is scalable, and their halide composition is tunable by simply using different combinations of precursor solutions. The versatility of the synthesis is demonstrated by applying it to relatively less explored shape-controlled synthesis of FAPbBr3 NCs. Despite the synthesis carried out in the air, both the inorganic and hybrid perovskite NCs exhibit nearly-narrow emission without applying any size-selective separation, and it is precisely tunable by controlling the reaction temperature. Financiado para publicación en acceso aberto: Universidade de Vigo/CISUG Ministerio de Ciencia, Innovación y Universidades | Ref. RYC2018-026103-I Agencia Estatal de Investigación | Ref. PID2020-117371RA-I00 Xunta de Galicia | Ref. ED431F2021/05 Xunta de Galicia | Ref. ED431C2020/09 Ministerio de Economía, Industria y Competitividad | Ref. BES-2017-081670

Many efforts have been directed towards elucidating the nitrogenase structure, its biocatalytic activity, and methods to artificially activate it by external stimuli. Here, we investigated how semiconductor nanoparticles (NPs) with sizes ranging between 2.3-3.5 nm form nano-biohybrids with the nitrogenase enzyme and enable its photoinduced biocatalytic activity. We examined two homogenously synthesized quantum dots (QDs), CdS, CdSe, and two nitrogenase variants, the wild-type and a cysteine-mutated. We show that the cysteine-mutated variant does not enhance the hydrogen generation amounts, as compared with the wild type. Nevertheless, we show that the 2.3 nm-sized CdSe NPs facilitate an eightfold increase compared with larger CdSe NPs. The obtained results were investigated using electrochemical techniques, transmission electron microscopy, and further confirmed by time-resolved spectroscopic measurements, which allow us to determine the electron tranfer rate constant (kET ) of the different configurations.

As one of the most ubiquitous bulk reagents available, the intrinsic chemical inertness of tetrahydrofuran (THF) makes direct and site-selective C(sp 3 )-H bond activation difficult, especially under redox neutral condition. Here, we demonstrate that semiconductor quantum dots (QDs) can activate α-C-H bond of THF via forming QDs/THF conjugates. Under visible light irradiation, the resultant alkoxyalkyl radical directly engages in radical cross-coupling with α-amino radical from amino C-H bonds or radical addition with alkene or phenylacetylene, respectively. In contrast to stoichiometric oxidant or hydrogen atom transfer reagents required in previous studies, the scalable benchtop approach can execute α-C-H bond functionalization of THF only by a QD photocatalyst under redox-neutral condition, thus providing a broad of value added chemicals starting from bulk THFs reagent. The high step- and atom-economy, high efficiency and broad substrate scope make the photocatalysis with QDs and visible light promising in both academic and industrial setting.

Juices, wines, and extracts from plants contain high concentrations of various chiral compounds such as carboxylic acids or sugars. Several prior studies reported the synthesis of metallic and semiconducting nanoparticles relying on components of complex biological solutions. Herein, we present preparation of chiral CdS and CdSe quantum dots (QDs) using apple juice and red wine via phase transfer ligand exchange. Although both apple juice and red wine contain a complex mixture of chiral and achiral compounds, we have successfully used them for selective induction of predicted chiroptical properties and confirmed L-malic acid from the apple juice and L-tartaric acid from the red wine as the chiral inducers. This work illustrates the capability of using complex mixtures to construct chiral QDs with desired chiroptical properties as well as potential of QDs to selectively report a chiral molecule in a complex chiral mixture without the need for elaborate chiral recognition system.

The development of fluorescence labeling techniques has attracted widespread interest in various fields, including biomedical science as it can facilitate high-resolution imaging and the spatiotemporal understanding of various biological processes. We report a supramolecular fluorescence labeling strategy using luminescent metal-phenolic networks (MPNs) constructed from metal ions, phenolic ligands, and common and commercially available dyes. The rapid labeling process (

The oxidative cleavage of C=C bonds is an important chemical reaction, which is a popular reaction in the photocatalytic field. However, high catalyst-loading and low turnover number (TON) are general shortcomings in reported visible-light-driven reactions. Herein, the direct oxidative cleavage of C=C bonds through water-soluble CdSe quantum dots (QDs) is described under visible-light irradiation at room temperature with high TON (up to 3.7×104 ). Under the same conditions, water-soluble CdSe QDs could also oxidize sulfides to sulfoxides with 51-84 % yields and TONs up to 3.4×104 . The key features of this photocatalytic protocol include high TONs, wide substrates scope, low catalyst loadings, simple and mild reaction conditions, and molecular O2 as the oxidant.

Precise control of the local electronic structure and properties of electrocatalysts is important for enhancing the multifunctionality and durability of electrocatalysts and for correlating the structure/chemistry with the catalytic properties. Herein, we report electronically coupled metallic hybrids of NiFe layered double hydroxide nanosheet/Ti3C2 MXene quantum dots deposited on a nitrogen‐doped graphene surface (LDH/MQD/NG) for high‐performance flexible Zn–air batteries (ZABs). As verified from the Mott–Schottky and Nyquist plots, as well as spectroscopic, electrochemical, and computational analyses, the electronic and chemical coupling of LDH/MQD/NG modulates the local electronic and surface structure of the active LDH to provide metallic conductivity and abundant active sites, leading to significantly improved bifunctional activity and electrocatalytic kinetics. The rechargeable ZABs with LDH/MQD/NG hybrids are superior to the previous LDH‐based ZABs, demonstrating a high power density (113.8 mW cm−2) and excellent cycle stability (150 h at 5 mA cm−2). Moreover, the corresponding quasi solid‐state ZABs are completely flexible and practical, affording a high power density of 57.6 mW cm−2 even in the bent state, and in real‐life operation of tandem cells for powering various electronic devices.

An effective path to synthesize Znx Cd1-x S quantum dots (ZCS QDs) in aqueous phase at room temperature has remained relatively unexplored. Here, we developed a room-temperature, aqueous-phase approach to ZCS QDs, using 3-mercaptopropionic acid (MPA) to adjust the pH of the reaction precursor solution to regulate the competition between sulfur source and hydroxyl group, and realize the large-scale preparation of water-soluble ZCS QDs photocatalyst at room temperature. Without recombination with other materials, and only by regulating the ratio of pH, excess sulfur sources and Zn/Cd, the photocatalytic degradation of rhodamine B (RhB) can reach 98% within 1 min, showing high photocatalytic activity. ZCS QDs show high stability and recoverability, and are expected to be able to deal with organic pollutants on a large scale. This study provides a new idea for the preparation of other QDs at room temperature.

Recently graphene quantum dot (GQD) based nanohybrid materials have received much attention. Herein, a highly fluorescent biocompatible GQD and N-functionalized dithienopyrrole (DTP-PPD) modified nanohybrid system was fabricated (DTP-PPD-fn-GQD) for the first time. Modification resulted in stable fluorescence with a quantum yield of approximately 22% and 36 nm redshift compared to unmodified GQD. The apparent bandgap tuning along with fluorescence property changes was investigated by cyclic voltammetry measurements and density functional theory studies. This water-soluble system was then applied for the sensitive and selective detection of Pb2+ ions. As a result of a specific interaction towards Pb2+ ions, the fluorescence intensity was quenched. The detection limit is found to be 1.02 nM within the linear range of 3 to 30 nM. Finally, the feasibility of the developed probe was tested with real samples of water. Chemically modified GQDs are already widely exploited for Pb2+ sensing, whereas GQD/thiophene-based nanohybrid systems are less utilized. This newly developed nanohybrid of GQD (DTP-PPD-fn-GQD) has excellent fluorescence properties and bandgap tunability. Moreover, effective fluorometric sensing of Pb2+ ions in an aqueous medium is well investigated. This gives more insight into developing GQD-based highly promising nanohybrid colorimetric as well as fluorescent sensors.

The study of nanocrystal self-assembly into superlattices or superstructures is of great significance in nanoscience. Carbon nitride quantum dots (CNQDs), being a promising new group of nanomaterials, however, have hardly been explored in their self-organizing behavior. Here we report of a unique irradiation-triggered self-assembly and recrystallization phenomenon of crystalline CNQDs (c-CNQDs) terminated by abundant oxygen-containing groups. Unlike the conventional self-assembly of nanocrystals into ordered superstructures, the photoinduced self-assembly of c-CNQDs resembles a "click reaction" process of macromolecules, in which the activated -OH and -NH 2 functional groups along the perimeters initiate cross-linking of adjacent QDs through a photocatalytic effect. Our findings unveil fundamental physiochemical features of CNQDs and open up new possibilities of manipulating carbon nitride nanomaterials via controlled assembly. Prospects for potential applications are discussed as well.

We introduce a new approach to transient spectroscopy, fluorescence‐detected pump–probe (F‐PP) spectroscopy, that overcomes several limitations of traditional PP. F‐PP suppresses excited‐state absorption, provides background‐free detection, removes artifacts resulting from pump–pulse scattering, from non‐resonant solvent response, or from coherent pulse overlap, and allows unique extraction of excited‐state dynamics under certain conditions. Despite incoherent detection, time resolution of F‐PP is given by the duration of the laser pulses, independent of the fluorescence lifetime. We describe the working principle of F‐PP and provide its theoretical description. Then we illustrate specific features of F‐PP by direct comparison with PP, theoretically and experimentally. For this purpose, we investigate, with both techniques, a molecular squaraine heterodimer, core–shell CdSe/ZnS quantum dots, and fluorescent protein mCherry. F‐PP is broadly applicable to chemical systems in various environments and in different spectral regimes., Ultrafast pump–probe spectroscopy detected by fluorescence is introduced. Combining sensitive fluorescence detection with ultrafast pulse‐limited time resolution, this approach provides a complementary technique to standard transient absorption.

A novel nitrogen-doped graphene quantum dots (N-GQDs) with a green fluorescence emission was synthesized through microwave method using citric acid and semicarbazide hydrochloride as reactants. The as-synthesized N-GQDs exhibited good stability, excellent water solubility, and negligible cytotoxicity. Due to intermolecular charge transfer, ferric ion (Fe3+ ) has a strong quenching effect on the N-GQDs. Fluorescence quenching has a linear relationship with the Fe3+ concentration in the range 0.02-12 μM. The detection limit was 1.43 nM. What is more, it is worth mentioning that the obtained N-GQDs showed high selectivity and sensitivity towards Fe3+ . Under the optimum conditions, the addition of 10-fold copper ions and 100-fold other metal ions had no influence on the detection of Fe3+ (0.8 μM), which indicated a higher sensitivity compared with that of the reported methods. Due to their excellent properties, the obtained N-GQDs was successfully applied for sensing and imaging Fe3+ in water samples and HeLa cells.

Solution-processed NiOx thin films have been applied as hole-injection layers (HILs) in quantum-dot light-emitting diodes (QLEDs). The commonly used NiOx HILs are prepared by the precursor-based route, which requires high annealing temperatures of over 275 °C to in situ convert the precursors into oxide films. Such high processing temperatures of NiOx HILs hinder their applications in flexible devices. Herein, we report a low-temperature approach based on Cu-modified NiOx (NiOx -Cu) nanocrystals to prepare HILs. A simple post-synthetic surface-modification step, which anchors the copper agents onto the surfaces of oxide nanocrystals, is developed to improve the electrical conductivity of the low-temperature-processed (135 °C) oxide-nanocrystal thin films. In consequence, QLEDs based on the NiOx -Cu HILs exhibit an external quantum efficiency of 17.5 % and a T95 operational lifetime of ∼2,800 h at an initial brightness of 1,000 cd m-2 , meeting the commercialization requirements for display applications. The results shed light on the potential of using NiOx -Cu HILs for realizing high-performance flexible QLEDs.

Herein, we first designed a one‐step strategy to achieve matrix‐free room temperature phosphorescence (RTP) materials by low temperature solid phase synthesis, using sodium citrate as carbon source and urea as nitrogen source. The NaF, NaCl, NaBr, and NaI were chosen as the inducer source of halogens to effective trigger the RTP emission from graphitic carbon nitride quantum dots (CNQDs) denoted F‐CNQDs, Cl‐CNQDs, Br‐CNQDs and I‐CNQDs. All the doped‐CNQDs emitted bright fluorescence upon 365 nm irradiation. After the 365 nm UV lamp is off, only the Br‐CNQDs showed green phosphorescence which can be observed by naked eye. The phosphorescence emission of Br‐CNQDs is excitation‐dependent from 510 to 610 nm with the average RTP lifetime of 70 milliseconds, which indicated Br‐CNQDs could exhibit color‐tunable phosphorescence. When 365 nm UV is off, Br‐CNQDs emitted green afterglow for about 3 seconds observed naked eye, while the Br‐CNQDs presented visible yellow afterglow for about 3 seconds with ceasing off 395 nm irradiation. The absolute phosphorescence quantum yield (PQY) of the Br‐CNQDs powder reaches up to 3.64%. Thus, the color change and long lifetime of phosphorescence from the excitation‐dependent feature could provide a security application for counterfeiting and information protection systems.