Nanoparticle-Doped Hybrid Polyelectrolyte Microcapsules with Controlled Photoluminescence for Potential Bioimaging Applications.

Fluorescent imaging is widely used in the diagnosis and tracking of the distribution, interaction, and transformation processes at molecular, cellular, and tissue levels. To be detectable, delivery systems should exhibit a strong and bright fluorescence. Quantum dots (QDs) are highly photostable fluorescent semiconductor nanocrystals with wide absorption spectra and narrow, size-tunable emission spectra, which make them suitable fluorescent nanolabels to be embedded into microparticles used as bioimaging and theranostic agents. The layer-by-layer deposition approach allows the entrapping of QDs, resulting in bright fluorescent microcapsules with tunable surface charge, size, rigidity, and functional properties. Here, we report on the engineering and validation of the structural and photoluminescent characteristics of nanoparticle-doped hybrid microcapsules assembled by the deposition of alternating oppositely charged polyelectrolytes, water-soluble PEGylated core/shell QDs with a cadmium selenide core and a zinc sulfide shell (CdSe/ZnS), and carboxylated magnetic nanoparticles (MNPs) onto calcium carbonate microtemplates. The results demonstrate the efficiency of the layer-by-layer approach to designing QD-, MNP-doped microcapsules with controlled photoluminescence properties, and pave the way for the further development of next-generation bioimaging agents based on hybrid materials for continuous fluorescence imaging.

Anisotropic nanomaterials for asymmetric synthesis.

The production of enantiopure chemicals is an essential part of modern chemical industry. Hence, the emergence of asymmetric catalysis led to dramatic changes in the procedures of chemical synthesis, and now it provides the most advantageous and economically executable solution for large-scale production of chiral chemicals. In recent years, nanostructures have emerged as potential materials for asymmetric synthesis. Indeed, on the one hand, nanomaterials offer great opportunities as catalysts in asymmetric catalysis, due to their tunable absorption, chirality, and unique energy transfer properties; on the other hand, the advantages of the larger surface area, increased number of unsaturated coordination centres, and more accessible active sites open prospects for catalyst encapsulation, partial or complete, in a nanoscale cavity, pore, pocket, or channel leading to alteration of the chemical reactivity through spatial confinement. This review focuses on anisotropic nanomaterials and considers the state-of-the-art progress in asymmetric synthesis catalysed by 1D, 2D and 3D nanostructures. The discussion comprises three main sections according to the nanostructure dimensionality. We analyze recent advances in materials and structure development, discuss the functional role of the nanomaterials in asymmetric synthesis, chirality, confinement effects, and reported enantioselectivity. Finally, the new opportunities and challenges of anisotropic 1D, 2D, and 3D nanomaterials in asymmetric synthesis, as well as the future prospects and current trends of the design and applications of these materials are analyzed in the Conclusions and outlook section.

Optimizing the PMMA Electron-Blocking Layer of Quantum Dot Light-Emitting Diodes.

Quantum dots (QDs) are promising candidates for producing bright, color-pure, cost-efficient, and long-lasting QD-based light-emitting diodes (QDLEDs). However, one of the significant problems in achieving high efficiency of QDLEDs is the imbalance between the rates of charge-carrier injection into the emissive QD layer and their transport through the device components. Here we investigated the effect of the parameters of the deposition of a poly (methyl methacrylate) (PMMA) electron-blocking layer (EBL), such as PMMA solution concentration, on the characteristics of EBL-enhanced QDLEDs. A series of devices was fabricated with the PMMA layer formed from acetone solutions with concentrations ranging from 0.05 to 1.2 mg/mL. The addition of the PMMA layer allowed for an increase of the maximum luminance of QDLED by a factor of four compared to the control device without EBL, that is, to 18,671 cd/m2, with the current efficiency increased by an order of magnitude and the turn-on voltage decreased by ~1 V. At the same time, we have demonstrated that each particular QDLED characteristic has a maximum at a specific PMMA layer thickness; therefore, variation of the EBL deposition conditions could serve as an additional parameter space when other QDLED optimization approaches are being developed or implied in future solid-state lighting and display devices.

Quantum Dot-Polyfluorene Composites for White-Light-Emitting Quantum Dot-Based LEDs.

Colloidal quantum dots (QDs) are a promising luminescent material for the development of next generation hybrid light-emitting diodes (QDLEDs). In particular, QDs are of great interest in terms of the development of solid-state light sources with an emission spectrum that mimics daylight. In this study, we used CdSe(core)/ZnS/CdS/ZnS(shell) QDs with organic ligands mimicking polyfluorene and its modified derivatives to obtain QD-polymer composites emitting white light. We found that the emission of the composites obtained by spin-coating, being strongly dependent on the chemical structure of the polymer matrix and the QD-to-polymer mass ratio, can be accurately controlled and adjusted to bring its emission spectrum close to the spectrum of daylight (CIE coordinates: 1931 0.307; 0.376). Moreover, the light emission of these composites has been found to be temporally stable, which is due to the minimal structural instability and volume-uniform charge and energy transfer properties. Thus, the use of the synthesized polyfluorene-based organic ligands with controllable chemical structures adaptable to the structure of the polymer matrix can significantly increase the stability of white light emission from QD composites, which can be considered promising electroluminescent materials for fabrication of white QDLEDs.

Al-, Ga-, Mg-, or Li-doped zinc oxide nanoparticles as electron transport layers for quantum dot light-emitting diodes.

Colloidal quantum dots and other semiconductor nanocrystals are essential components of next-generation lighting and display devices. Due to their easily tunable and narrow emission band and near-unity fluorescence quantum yield, they allow cost-efficient fabrication of bright, pure-color and wide-gamut light emitting diodes (LEDs) and displays. A critical improvement in the quantum dot LED (QLED) technology was achieved when zinc oxide nanoparticles (NPs) were first introduced as an electron transport layer (ETL) material, which tremendously enhanced the device brightness and current efficiency due to the high mobility of electrons in ZnO and favorable alignment of its energy bands. During the next decade, the strategy of ZnO NP doping allowed the fabrication of QLEDs with a brightness of about 200 000 cd/m2 and current efficiency over 60 cd/A. On the other hand, the known ZnO doping approaches rely on a very fine tuning of the energy levels of the ZnO NP conduction band minimum; hence, selection of the appropriate dopant that would ensure the best device characteristics is often ambiguous. Here we address this problem via detailed comparison of QLEDs whose ETLs are formed by a set of ZnO NPs doped with Al, Ga, Mg, or Li. Although magnesium-doped ZnO NPs are the most common ETL material used in recently designed QLEDs, our experiments have shown that their aluminum-doped counterparts ensure better device performance in terms of brightness, current efficiency and turn-on voltage. These findings allow us to suggest ZnO NPs doped with Al as the best ETL material to be used in future QLEDs.