The influence of solvent refractive index on the photoluminescence decay of thick-shell gradient-alloyed colloidal quantum dots investigated in a wide range of delay times.

Colloidal semiconductor quantum dots have many potential optical applications, including quantum dot light-emitting diodes, single-photon sources, or biological luminescent markers. The optical properties of colloidal quantum dots can be affected by their dielectric environment. This study investigated the photoluminescence (PL) decay of thick-shell gradient-alloyed colloidal semiconductor quantum dots as a function of solvent refractive index. These measurements were conducted in a wide range of delay times to account for both the initial spontaneous decay of excitons and the delayed emission of excitons that has the form of a power law. It is shown that whereas the initial spontaneous PL decay is very sensitive to the refractive index of the solvent, the power-law delayed emission of excitons is not. Our results seem to exclude the possibility of carrier self-trapping in the considered solvents and suggest the existence of trap states inside the quantum dots. Finally, our data show that the average exciton lifetime significantly decreases as a function of the solvent refractive index. The change in exciton lifetime is qualitatively modeled and discussed.

Flexible Quantum-Dot Light-Emitting Diodes Using Embedded Silver Mesh Transparent Electrodes Manufactured by an Ultraprecise Deposition Method.

Transparent conductive electrodes (TCEs) fabricated onto flexible substrates are crucial parts of organic-light-emitting diodes (OLEDs), which are vastly utilized for display and lightning applications. Indium tin oxide (ITO), which is so far the most popular material for transparent and conductive electrodes, is found to be an unsuitable candidate for flexible devices mostly due to its brittleness. Here, we present a novel approach for the fabrication of transparent, conductive, and flexible electrodes for optoelectronic applications made of silver metal mesh by an ultraprecise deposition (UPD) method. The fabricated mesh exhibits an 80% (λ = 550 nm) optical transmittance and a sheet resistance of 11 Ω/sq. The Ag-mesh embedded into the polymer is implemented as an anode for a quantum-dot light-emitting diode (QLED) in order to assess its performance. The fabricated QLED is characterized by the maximum external quantum efficiency (EQE) of 2% and a current efficiency (CE) of 6 cd/A, reaching the maximum luminance (L) of 3200 cd/m2 at a current density of 100 mA/cm2. This method shows a fast and relatively simple approach to fabricate optoelectronic devices without the need for special treatment and sophisticated equipment.

CdS Nanoplates Modification as a Platform for Synthesis of Blue-Emitting Nanoparticles.

In this paper, the study of surface modification of two-dimensional (2D), non-luminescent CdS nanoplates (NPLs) by thiol-containing ligands is presented. We show that a process of twophase transfers with appropriate ligand exchange transforms non-luminescent NPLs into spherical CdS nanoparticles (NPs) exhibiting a blue photoluminescence with exceptionally high quantum yield ~90%. In the process, transfer from inorganic solvent to water is performed, with appropriately selected ligand molecules and pH values (forward phase transfer), which produces NPs with modified size and shape. Then, in reverse phase transfer, NPs are transferred back to toluene due to surface modification by combined Cd (OL)2 and Cd (Ac)2. As a result, spherical NPs are formed (average diameter between 4 and 6 nm) with PL QY as high as 90%. This is unique for core only CdS NPs without inorganic shell.

Effect of Air Exposure of ZnMgO Nanoparticle Electron Transport Layer on Efficiency of Quantum-Dot Light-Emitting Diodes.

We demonstrate the effect of air exposure on optical and electrical properties of ZnMgO nanoparticles (NPs) typically exploited as an electron transport layer in Cd-based quantum-dot light-emitting diodes (QLEDs). We analyze the roles of air components in modifying the electrical properties of ZnMgO NPs, which reveals that H2O enables the reduction of hole leakage while O2 alters the character of charge transport due to its ability to trap electrons. As a result, the charge balance in the QDs layer is improved, which is confirmed by voltage-dependent measurements of photoluminescence quantum yield. The maximum external quantum efficiency is improved over 2-fold and reaches the value of 9.5% at a luminance of 104 cd/m2. In addition, we investigate the problem of electron leakage into the hole transport layer and show that trap-mediated electron transport in the ZnMgO layer caused by adsorbed O2 ensures a higher leakage threshold. This work also provides an insight into the possible disadvantages of device contact with air as well as problems and challenges that might occur during open-air fabrication of QLEDs.

CdS Dots, Rods and Platelets-How to Obtain Predefined Shapes in a One-Pot Synthesis of Nanoparticles.

In recent years, numerous protocols for nanoplatelet synthesis have been developed. Here, we present a facile, one-pot method for controlling cadmium sulfide (CdS) nanoparticles' shape that allows for obtaining zero-dimensional, one-dimensional, or two-dimensional structures. The proposed synthesis protocol is a simple heating-up approach and does not involve any inconvenient steps such as injection and/or pouring the precursors at elevated temperatures. Because of this, the synthesis protocol is highly repeatable. A gradual increase in the zinc acetate concentration causes the particles' shape to undergo a transition from isotropic quantum dots through rods to highly anisotropic nanoplatelets. We identified conditions at which synthesized platelets were purely five monolayers thick. All samples acquired during different stages of the reaction were characterized via optical spectroscopy, which allowed for the identification of the presence of high-temperature, magic-size clusters prior to the platelets' formation.

pH-dependent fluorescence of thiol-coated CdSe/CdS quantum dots in an aqueous phase.

The results presented in this paper show how the optical properties and colloidal stability of quantum dots (QDs) vary depending on pH conditions. For this investigation, as-synthesized hydrophobic CdSe/CdS QDs were transferred to an aqueous medium by surface modification with 3-mercaptopropionic acid. The ligand exchange procedure was applied under three different pH conditions: acidic, neutral and alkaline, to obtain three kinds of hydrophilic QDs dispersed in phosphate buffer. The efficiency of the functionalization of QDs was estimated based on the changes in ABS and the highest value was obtained under acidic conditions (45%). The efficiency of photoluminescence (PL) was also best preserved under these conditions, although it was 30 times less than the PL of hydrophobic QDs. Then, all three kinds of hydrophilic QDs were dispersed in solutions with a wide range of pH (2-12) and investigated by absorbance and PL measurements. The results show that QDs subjected to a ligand exchange procedure are characterized by intensive PL at the selected pH values, which correspond to pKa of the ligand. This phenomenon is independent of the pH at which the ligand exchange procedure is conducted. Moreover, it was found that the PL intensity is preserved during the experiment for QDs functionalized under neutral conditions, whereas it decreases for acidic and increases for alkaline conditions.

Highly colloidally stable trimodal 125I-radiolabeled PEG-neridronate-coated upconversion/magnetic bioimaging nanoprobes.

"All-in-one" multifunctional nanomaterials, which can be visualized simultaneously by several imaging techniques, are required for the efficient diagnosis and treatment of many serious diseases. This report addresses the design and synthesis of upconversion magnetic NaGdF4:Yb3+/Er3+(Tm3+) nanoparticles by an oleic acid-stabilized high-temperature coprecipitation of lanthanide precursors in octadec-1-ene. The nanoparticles, which emit visible or UV light under near-infrared (NIR) irradiation, were modified by in-house synthesized PEG-neridronate to facilitate their dispersibility and colloidal stability in water and bioanalytically relevant phosphate buffered saline (PBS). The cytotoxicity of the nanoparticles was determined using HeLa cells and human fibroblasts (HF). Subsequently, the particles were modified by Bolton-Hunter-neridronate and radiolabeled by 125I to monitor their biodistribution in mice using single-photon emission computed tomography (SPECT). The upconversion and the paramagnetic properties of the NaGdF4:Yb3+/Er3+(Tm3+)@PEG nanoparticles were evaluated by photoluminescence, magnetic resonance (MR) relaxometry, and magnetic resonance imaging (MRI) with 1 T and 4.7 T preclinical scanners. MRI data were obtained on phantoms with different particle concentrations and during pilot long-time in vivo observations of a mouse model. The biological and physicochemical properties of the NaGdF4:Yb3+/Er3+(Tm3+)@PEG nanoparticles make them promising as a trimodal optical/MRI/SPECT bioimaging and theranostic nanoprobe for experimental medicine.

Single-Nanocrystal Studies on the Homogeneity of the Optical Properties of NaYF4:Yb3+,Er3.

Development of upconverting nanomaterials which are able to emit visible light upon near-infrared excitation opens a wide range of potential applications. Because of their remarkable photostability, they are widely used in bioimaging, optogenetics, and optoelectronics. In this work, we demonstrate the influence of several experimental conditions as well as a dopant concentration on the luminescence properties of upconverting nanocrystals (UPNCs) that need to be taken into account for their efficient use in the practical applications. We found that not only nanoparticle architecture affects the optical properties of UPNCs, but also factors such as sample concentration, excitation light power density, and temperature may influence the green-to-red emission ratio. We performed studies on both the single-nanoparticle and ensemble levels over a broad concentration range and found the heterogeneity in the optical properties of UPNCs with low dopant concentrations.

Monodisperse Core-Shell NaYF4:Yb3+/Er3+@NaYF4:Nd3+-PEG-GGGRGDSGGGY-NH2 Nanoparticles Excitable at 808 and 980 nm: Design, Surface Engineering, and Application in Life Sciences.

Lanthanide-doped upconversion nanoparticles (UCNPs) have a unique capability of upconverting near-infrared (NIR) excitation into ultraviolet, visible, and NIR emission. Conventional UCNPs composed of NaYF4:Yb3+/Er3+(Tm3+) are excited by NIR light at 980 nm, where undesirable absorption by water can cause overheating or damage of living tissues and reduce nanoparticle luminescence. Incorporation of Nd3+ ions into the UCNP lattice shifts the excitation wavelength to 808 nm, where absorption of water is minimal. Herein, core-shell NaYF4:Yb3+/Er3+@NaYF4:Nd3+ nanoparticles, which are doubly doped by sensitizers (Yb3+ and Nd3+) and an activator (Er3+) in the host NaYF4 matrix, were synthesized by high-temperature coprecipitation of lanthanide chlorides in the presence of oleic acid as a stabilizer. Uniform core (24 nm) and core-shell particles with tunable shell thickness (~0.5-4 nm) were thoroughly characterized by transmission electron microscopy (TEM), energy-dispersive analysis, selected area electron diffraction, and photoluminescence emission spectra at 808 and 980 nm excitation. To ensure dispersibility of the particles in biologically relevant media, they were coated by in-house synthesized poly(ethylene glycol) (PEG)-neridronate terminated with an alkyne (Alk). The stability of the NaYF4:Yb3+/Er3+@NaYF4:Nd3+-PEG-Alk nanoparticles in water or 0.01 M PBS and the presence of PEG on the surface were determined by dynamic light scattering, ζ-potential measurements, thermogravimetric analysis, and FTIR spectroscopy. Finally, the adhesive azidopentanoyl-modified GGGRGDSGGGY-NH2 (RGDS) peptide was immobilized on the NaYF4:Yb3+/Er3+@NaYF4:Nd3+-PEG-Alk particles via Cu(I)-catalyzed azide-alkyne cycloaddition. The toxicity of the unmodified core-shell NaYF4:Yb3+/Er3+@NaYF4:Nd3+, NaYF4:Yb3+/Er3+@NaYF4:Nd3+-PEG-Alk, and NaYF4:Yb3+/Er3+@NaYF4:Nd3+-PEG-RGDS nanoparticles on both Hep-G2 and HeLa cells was determined, confirming no adverse effect on their survival and proliferation. The interaction of the nanoparticles with Hep-G2 cells was monitored by confocal microscopy at both 808 and 980 nm excitation. The NaYF4:Yb3+/Er3+@NaYF4:Nd3+-PEG-RGDS nanoparticles were localized on the cell membranes due to specific binding of the RGDS peptide to integrins, in contrast to the NaYF4:Yb3+/Er3+@NaYF4:Nd3+-PEG-Alk particles, which were not engulfed by the cells. The NaYF4:Yb3+/Er3+@NaYF4:Nd3+-PEG-RGDS nanoparticles thus appear to be promising as a new non-invasive probe for specific bioimaging of cells and tissues. This development makes the nanoparticles useful for diagnostic and/or, after immobilization of a bioactive compound, even theranostic applications in the treatment of various fatal diseases.

Synergistic effect of methylene blue and biogenic gold nanoparticles against Enterococcus faecalis.

This study reports successful photodynamic inactivation of planktonic and biofilm cells of Enterococcus faecalis using Methylene Blue (MB) in combination with gold nanoparticles synthesized using the cell-free filtrate obtained from 3-day biomass of Trichoderma asperellum strain. Monodispersed colloidal gold nanoparticles were characterized by UV-vis absorption, TEM and DLS to be 13 ±â€¯3 nm spheres. Diode lasers with the peak-power wavelength ʎ = 660 nm (output power of 21, 41 and 68 mW; power density of 55, 108 and 179 mW∙cm-2, respectively, were used as a light source to study the effects of MB alone, the gold nanoparticles alone (AuNPs) and the MB + AuNPs mixture on the viability of E. faecalis cells. The lethal effect of planktonic cells was achieved for MB after 30 min of laser irradiation with energy fluence of 322 J∙cm-2. When MB + AuNPs mixture was used as photosensitizer, the lethal effect was achieved with energy fluence of 292 J∙cm-2. The biofilm culture was more resistant to photo-inactivation and the best bactericidal effect of MB as photosensitizer was found after light dose of 483 J∙cm-2. The bacterial cell viability was reduced by 99.92%. It was proved that MB + AuNPs mixture synergistically enhances the kill of the studied microorganism as the same light dose resulted in 99.991% kill.

Optical Sensors Based on II-VI Quantum Dots.

Fundamentals of quantum dots (QDs) sensing phenomena show the predominance of these fluorophores over standard organic dyes, mainly because of their unique optical properties such as sharp and tunable emission spectra, high emission quantum yield and broad absorption. Moreover, they also indicate no photo bleaching and can be also grown as no blinking emitters. Due to these properties, QDs may be used e.g., for multiplex testing of the analyte by simultaneously detecting multiple or very weak signals. Physico-chemical mechanisms used for analyte detection, like analyte stimulated QDs aggregation, nonradiative Förster resonance energy transfer (FRET) exhibit a number of QDs, which can be applied in sensors. Quantum dots-based sensors find use in the detection of ions, organic compounds (e.g., proteins, sugars, volatile substances) as well as bacteria and viruses.

Quantum-dot light-emitting diode with ultrathin Au electrode embedded in solution-processed phosphomolybdic acid.

We proposed to exploit phosphomolybdic acid (PMA) as a cost-efficient MoO x source for combined spin-coating/sputtering/spin-coating deposition of a MoO x /Au/MoO x (MAM) composite electrode. The bottom PMA layer provides perfect wetting conditions for ultrathin Au film sputtering and prevents the formation of gold islands on the glass surface, while the top PMA layer helps to reduce light reflection. By optimizing the thickness of ultrathin Au films and PMA layers, we achieved maximum transmittance of 79% at 550 nm and a sheet resistance of only 22 Ω sq-1 which is comparable to the resistance of ITO substrates (20 Ω sq-1). MAM multilayer was explored both as a transparent electrode and as a hole injection layer (HIL) to eliminate ITO and PEDOT:PSS from solution-processed quantum-dot light-emitting diodes (QLEDs). The fabricated MAM-based QLED shows a peak external quantum efficiency (EQE) of 2.7% and maximum brightness of 12 000 cd m-2 at 7 V. By performing bending tests of the polyethylene (PET) substrate coated with MAM electrode, we demonstrate that it is also a promising candidate for flexible transparent optoelectronics.

Phthalocyanine-Conjugated Upconversion NaYF4 :Yb3+ /Er3+ @SiO2 Nanospheres for NIR-Triggered Photodynamic Therapy in a Tumor Mouse Model.

Photodynamic therapy (PDT) has garnered immense attention as a minimally invasive clinical treatment modality for malignant cancers. However, its low penetration depth and photodamage of living tissues by UV and visible light, which activate a photosensitizer, limit the application of PDT. In this study, monodisperse NaYF4 :Yb3+ /Er3+ nanospheres 20 nm in diameter, that serve as near-infrared (NIR)-to-visible light converters and activators of a photosensitizer, were synthesized by high-temperature co-precipitation of lanthanide chlorides in a high-boiling organic solvent (octadec-1-ene). The nanoparticles were coated with a thin shell (≈3 nm) of homogenous silica via the hydrolysis and condensation of tetramethyl orthosilicate. The NaYF4 :Yb3+ /Er3+ @SiO2 particles were further functionalized by methacrylate-terminated groups via 3-(trimethoxysilyl)propyl methacrylate. To introduce a large number of reactive amino groups on the particle surface, methacrylate-terminated NaYF4 :Yb3+ /Er3+ @SiO2 nanospheres were modified with a branched polyethyleneimine (PEI) via Michael addition. Aluminum carboxyphthalocyanine (Al Pc-COOH) was then conjugated to NaYF4 :Yb3+ /Er3+ @SiO2 -PEI nanospheres via carbodiimide chemistry. The resulting NaYF4 :Yb3+ /Er3+ @SiO2 -PEI-Pc particles were finally modified with succinimidyl ester of poly(ethylene glycol) (PEG) in order to alleviate their future uptake by the reticuloendothelial system. Upon 980 nm irradiation, the intensive red emission of NaYF4 :Yb3+ /Er3+ @SiO2 -PEI-Pc-PEG nanoparticles completely vanished, indicating efficient energy transfer from the nanoparticles to Al Pc-COOH, which generates singlet oxygen (1 O2 ). Last but not least, NaYF4 :Yb3+ /Er3+ @SiO2 -PEI-Pc-PEG nanospheres were intratumorally administered into mammary carcinoma MDA-MB-231 growing subcutaneously in athymic nude mice. Extensive necrosis developed at the tumor site of all mice 24-48 h after irradiation by laser at 980 nm wavelength. The results demonstrate that the NaYF4 :Yb3+ /Er3+ @SiO2 -PEI-Pc-PEG nanospheres have great potential as a novel NIR-triggered PDT nanoplatform for deep-tissue cancer therapy.

Effects of surface functionalization of hydrophilic NaYF4 nanocrystals doped with Eu3+ on glutamate and GABA transport in brain synaptosomes.

Specific rare earth doped nanocrystals (NCs), a recent class of nanoparticles with fluorescent features, have great bioanalytical potential. Neuroactive properties of NaYF4 nanocrystals doped with Eu3+ were assessed based on the analysis of their effects on glutamate- and γ-aminobutyric acid (GABA) transport process in nerve terminals isolated from rat brain (synaptosomes). Two types of hydrophilic NCs were examined in this work: (i) coated by polyethylene glycol (PEG) and (ii) with OH groups at the surface. It was found that NaYF4:Eu3+-PEG and NaYF4:Eu3+-OH within the concentration range of 0.5-3.5 and 0.5-1.5 mg/ml, respectively, did not influence Na+-dependent transporter-dependent l-[14C]glutamate and [3H]GABA uptake and the ambient level of the neurotransmitters in the synaptosomes. An increase in NaYF4:Eu3+-PEG and NaYF4:Eu3+-OH concentrations up to 7.5 and 3.5 mg/ml, respectively, led to the (1) attenuation of the initial velocity of uptake of l-[14C]glutamate and [3H]GABA and (2) elevation of ambient neurotransmitters in the suspension of nerve terminals. In the mentioned concentrations, nanocrystals did not influence acidification of synaptic vesicles that was shown with pH-sensitive fluorescent dye acridine orange, however, decreased the potential of the plasma membrane of synaptosomes. In comparison with other nanoparticles studied with similar methodological approach, NCs start to exhibit their effects on neurotransmitter transport at concentrations several times higher than those shown for carbon dots, detonation nanodiamonds and an iron storage protein ferritin, whose activity can be registered at 0.08, 0.5 and 0.08 mg/ml, respectively. Therefore, NCs can be considered lesser neurotoxic as compared to above nanoparticles.

Size and shape effects in ß-NaGdF4: Yb3+, Er3+ nanocrystals.

Three sets of ß-NaGdF4:Yb3+, Er3+ nanocrystals (NCs) with different shapes (spherical and more complex flower shapes), different sizes (6-17 nm) and Yb3+ concentrations (2%-15%) were synthesized by a co-precipitation method using oleic acid as a stabilizing agent. The uncommon, single-crystalline flower-shaped NCs were obtained by simply adjusting the fluorine-to-lanthanides molar ratio. Additionally, some of the NCs with different sizes have been covered by the un-doped shell. The crystal phase, shapes and sizes of all NCs were examined using transmission electron microscopy and x-ray diffraction methods. Simultaneously, upconversion luminescence and lifetimes, under 980 nm excitation, were measured and the changes in green to red (G/R) emission ratios as well as emission decay times were correlated with the evolution of nanocrystal sizes and surface to volume ratios. Three different mechanisms responsible for the changes in G/R ratios were presented and discussed.

The effect of core and lanthanide ion dopants in sodium fluoride-based nanocrystals on phagocytic activity of human blood leukocytes.

Sodium fluoride-based ß-NaLnF4 nanoparticles (NPs) doped with lanthanide ions are promising materials for application as luminescent markers in bio-imaging. In this work, the effect of NPs doped with yttrium (Y), gadolinium (Gd), europium (Eu), thulium (Tm), ytterbium (Yb) and terbium (Tb) ions on phagocytic activity of monocytes and granulocytes and the respiratory burst was examined. The surface functionalization of <10-nm NPs was performed according to our variation of patent pending ligand exchange method that resulted in meso-2,3-dimercaptosuccinic acid (DMSA) molecules on their surface. Y-core-based NCs were doped with Eu ions, which enabled them to be excited with UV light wavelengths. Cultures of human peripheral blood (n = 8) were in vitro treated with five different concentrations of eight NPs for 24 h. In summary, neither type of nanoparticles is found toxic with respect to conducted test; however, some cause toxic effects (they have statistically significant deviations compared to reference) in some selected doses tested. Both core types of NPs (Y-core and Gd-core) impaired the phagocytic activity of monocytes the strongest, having minimal or none whatsoever influence on granulocytes and respiratory burst of phagocytic cells. The lowest toxicity was observed in Gd-core, Yb, Tm dopants and near-infrared nanoparticles. Clear dose-dependent effect of NPs on phagocytic activity of leukocytes and respiratory burst of cells was observed for limited number of samples.

Facile synthesis of phosphine free ultra-small PbSe nanocrystals and their light harvesting studies in ETA solar cells.

Ultra-small PbSe nanocrystals (NCs) were synthesized via a 'one-pot' approach in olive oil as the reaction medium and capping agent. The optical spectra showed discernible blue shifts in the absorption band edges (570-780 nm) due to strong quantum confinement effects and photoluminescence (PL) spectra showed significant strong emission peaks in the range of 780-850 nm. The broad peaks in the powder X-ray diffraction (p-XRD) pattern indicate the ultra-small size of the as-prepared NCs. These NCs were used to construct an extremely thin absorber (ETA) solar device after surface modification. The preliminary results indicate their potential as light harvesting entities in nanostructure based solar cells.

Hydrophobic sodium fluoride-based nanocrystals doped with lanthanide ions: assessment of in vitro toxicity to human blood lymphocytes and phagocytes.

In vitro immunotoxicity of hydrophobic sodium fluoride-based nanocrystals (NCs) doped with lanthanide ions was examined in this study. Although there is already a significant amount of optical and structural data on NaYF4 NCs, data on safety assessment are missing. Therefore, peripheral whole blood from human volunteers was used to evaluate the effect of 25 and 30 nm hydrophobic NaYF4 NCs dissolved in cyclohexane (CH) on lymphocytes, and of 10 nm NaYF4 NCs on phagocytes. In the concentration range 0.12-75 µg cm(-2) (0.17-106 µg ml(-1) ), both 25 and 30nm NaYF4 NCs did not induce cytotoxicity when measured as incorporation of [(3) H]-thymidine into DNA. Assessment of lymphocyte function showed significant suppression of the proliferative activity of T-lymphocytes and T-dependent B-cell response in peripheral blood cultures (n = 7) stimulated in vitro with mitogens phytohemagglutinin (PHA) and pokeweed (PWM) (PHA > PWM). No clear dose-response effect was observed. Phagocytic activity and respiratory burst of leukocytes (n = 5-8) were generally less affected. A dose-dependent suppression of phagocytic activity of granulocytes in cultures treated with 25 nm NCs was observed (vs. medium control). A decrease in phagocytic activity of monocytes was found in cells exposed to higher doses of 10 and 30 nm NCs. The respiratory burst of phagocytes was significantly decreased by exposure to the middle dose of 30 nm NCs only. In conclusion, our results demonstrate immunotoxic effects of hydrophobic NaYF4 NCs doped with lanthanide ions to lymphocytes and to lesser extent to phagocytes. Further research needs to be done, particularly faze transfer of hydrophobic NCs to hydrophilic ones, to eliminate the solvent effect.