ZnF2-Assisted Synthesis of Highly Luminescent InP/ZnSe/ZnS Quantum Dots for Efficient and Stable Electroluminescence.

High-quality InP-based quantum dots (QDs) have become very promising, environmentally benign light emitters for display applications, but their synthesis generally entails hazardous hydrofluoric acid. Here, we present a highly facile route to InP/ZnSe/ZnS core/shell/shell QDs with a near-unity photoluminescence quantum yield. As the key additive, the inorganic salt ZnF2 mildly reacts with carboxylic acid at a high temperature and in situ generates HF, which eliminates surface oxide impurities, thus facilitating epitaxial shell growth. The resulting InP/ZnSe/ZnS QDs exhibit a narrower emission line width and better thermal stability in comparison with QDs synthesized with hydrofluoric acid. Light-emitting diodes using large-sized InP/ZnSe/ZnS QDs without replacing original ligands achieve the highest peak external quantum efficiency of 22.2%, to the best of our knowledge, along with a maximum brightness of >110 000 cd/m2 and a T95 lifetime of >32 000 h at 100 cd/m2. This safe approach is anticipated to be applied for a wide range of III-V QDs.

Adverse events and preventive measures related to COVID-19 vaccines.

The coronavirus disease 2019 (COVID-19) vaccines are categorized according to the manufacturing technique, including mRNA vaccines and adenovirus vector vaccines. According to previous studies, the reported efficacy of the COVID-19 vaccine is excellent regardless of the type of vaccine, and the majority of studies have shown similar results for safety. Most of the adverse reactions after vaccination were mild or moderate grade, and severe reactions were reported in a very small proportion. However, the adverse reactions that might occur after nationwide vaccinations can contribute to crowding of emergency departments, and this can further lead to significant obstacles to providing necessary treatment for life-threatening conditions. Therefore, as emergency physicians, we would like to present some concerns and suggestions to prevent these predictable problems.

Comparison of emergency department utilization trends between the COVID-19 pandemic and control period.

ABSTRACT: Infectious disease pandemics has a great impact on the use of medical facilities. The purpose of this study was to analyze the effects of coronavirus disease 2019 (COVID-19) on the use of emergency medical facilities in the Republic of Korea. This single-center, retrospective observational study was conducted in a tertiary teaching hospital located in Incheon Metropolitan City, Republic of Korea. We set the pandemic period as February 19, 2020 to April 18, 2020, and the control period was set to the same period in 2018 and 2019. All consecutive patients who visited the emergency department (ED) during the study period were included. Patients were divided into 3 groups according to age (pediatric patients, younger adult patients and older adult patients). The total number, demographics, clinical data, and diagnostic codes of ED patients were analyzed. The total number of ED patients in the pandemic period was lower than that in the control period, which was particularly pronounced for pediatric patients. The proportion of patients who used the 119 ambulances increased in all 3 groups (P  = .002, P < .001, and P = .001), whereas the proportion of patients who visited on foot was decreased (P  = .006, P < .001, and P = .027). In terms of diagnostic codes, a significant decrease was observed in the proportion of certain infectious or parasitic diseases (A00-B99), and respiratory diseases (J00-J99) in the pediatric and younger adult patient groups (P < .001 and P < .001, respectively). The COVID-19 pandemic reduced the number of ED patients; however, the proportion of patients using ambulances increased. In particular, the proportion of patients with diagnostic codes for infectious and respiratory diseases significantly decreased during the pandemic period.

Unusual Hole Transfer Dynamics of the NiO Layer in Methylammonium Lead Tri-iodide Absorber Solar Cells.

Nickel oxides (NiO) as hole transport layers (HTLs) in inverted-type perovskite solar cells (PSCs) have been widely studied mainly because of their high stability under illumination. Increases in the power conversion efficiency (PCE) with NiO HTLs have been presented in numerous reports, although the photoluminescence (PL) quenching behavior does not coincide with the PCE increase. The dynamics of the charge carrier transport between the NiO HTLs and the organic-inorganic halide perovskite absorbers is not clearly understood yet and quite unusual, in contrast to organic/polymerics HTLs. We deposited NiO HTLs with precisely controlled thicknesses by atomic layer deposition (ALD) and studied their photovoltaic performances and hole transfer characteristics. Ground state bleaching (GSB) recovery was observed by ultrafast transient absorption spectroscopy (TAS), which suggested that backward hole injection occurred between the perovskites and NiO HTLs, so that the uncommon PL behaviors can be clearly explained. Backward hole injection from the NiO HTL to the perovskite absorber originated from their similar valence band (VB) energy positions. The thickness increase of the NiO HTLs induced VB sharing, which caused a red-shift of the photoinduced hole absorption spectrum in near-infrared (NIR) femtosecond TAS and a decrease in the PL intensity. Our studies on inorganic metal oxide transport layers, NiO in this work, with a thickness dependence and the comparison with organic layers provide a better understanding of the interfacial carrier dynamics in PSCs.

Bifacial Passivation of Organic Hole Transport Interlayer for NiO x -Based p-i-n Perovskite Solar Cells.

Methoxy-functionalized triphenylamine-imidazole derivatives that can simultaneously work as hole transport materials (HTMs) and interface-modifiers are designed for high-performance and stable perovskite solar cells (PSCs). Satisfying the fundamental electrical and optical properties as HTMs of p-i-n planar PSCs, their energy levels can be further tuned by the number of methoxy units for better alignment with those of perovskite, leading to efficient hole extraction. Moreover, when they are introduced between perovskite photoabsorber and low-temperature solution-processed NiO x interlayer, widely featured as an inorganic HTM but known to be vulnerable to interfacial defect generation and poor contact formation with perovskite, nitrogen and oxygen atoms in those organic molecules are found to work as Lewis bases that can passivate undercoordinated ion-induced defects in the perovskite and NiO x layers inducing carrier recombination, and the improved interfaces are also beneficial to enhance the crystallinity of perovskite. The formation of Lewis adducts is directly observed by IR, Raman, and X-ray photoelectron spectroscopy, and improved charge extraction and reduced recombination kinetics are confirmed by time-resolved photoluminescence and transient photovoltage experiments. Moreover, UV-blocking ability of the organic HTMs, the ameliorated interfacial property, and the improved crystallinity of perovskite significantly enhance the stability of PSCs under constant UV illumination in air without encapsulation.

Formation and Encapsulation of All-Inorganic Lead Halide Perovskites at Room Temperature in Metal-Organic Frameworks.

Improving the stability and tuning the optical properties of semiconducting perovskites are vital for their applications in advanced optoelectronic devices. We present a facile synthetic method for hybrid composites of perovskites and metal-organic frameworks (MOFs). A simple two-step solution-based method without organic surfactants was employed to make all-inorganic lead-halide perovskites (CsPbX3; X = Cl, Br, I, or mixed halide compositions) form directly in the pores of MIL-101 MOF. That is, a polar organic solution of lead halide (PbX2) was impregnated into the MOF pores to give PbX2@MIL-101, which was then subjected to a perovskite-formation reaction with cesium halide (CsX) dissolved in methanol. The compositions of the halogen anions in the perovskites can be modulated with various halide precursors, leading to CsPbX3@MIL-101 composites with X3 = Cl3, Cl2Br, Br2Cl, Br3, Br2I, I2Br, and I3 that exhibit gradual variation of band gap energies and tuned emission wavelengths from 417 to 698 nm.

Management of transition dipoles in organic hole-transporting materials under solar irradiation for perovskite solar cells.

In organic hole-transporting material (HTM)-based p-i-n planar perovskite solar cells, which have simple and low-temperature processibility feasible to flexible devices, the incident light has to pass through the HTM before reaching the perovskite layer. Therefore, photo-excited state of organic HTM could become important during the solar cell operation, but this feature has not usually been considered for the HTM design. Here, we prove that enhancing their property at their photo-excited states, especially their transition dipole moments, can be a methodology to develop high efficiency p-i-n perovskite solar cells. The organic HTMs are designed to have high transition dipole moments at the excited states and simultaneously to preserve those property during the solar cell operation by their extended lifetimes through the excited-state intramolecular proton transfer process, consequently reducing the charge recombination and improving extraction properties of devices. Their UV-filtering ability is also beneficial to enhance the photostability of devices.

High-Efficiency Air-Stable Colloidal Quantum Dot Solar Cells Based on a Potassium-Doped ZnO Electron-Accepting Layer.

High-efficiency colloidal quantum dot (CQD) solar cells (CQDSCs) with improved air stability were developed by employing potassium-modified ZnO as an electron-accepting layer (EAL). The effective potassium modification was achievable by a simple treatment with a KOH solution of pristine ZnO films prepared by a low-temperature solution process. The resulting K-doped ZnO (ZnO-K) exhibited EAL properties superior to those of a pristine ZnO-EAL. The Fermi energy level of ZnO was upshifted, which increased the internal electric field and amplified the depletion region (i.e., charge drift) of the devices. The surface defects of ZnO were effectively passivated by K modification, which considerably suppressed interfacial charge recombination. The CQDSC based on ZnO-K achieved improved power conversion efficiency (PCE) of ≈10.75% ( VOC of 0.67 V, JSC of 23.89 mA cm-2, and fill factor of 0.68), whereas the CQDSC based on pristine ZnO showed PCE of 9.97%. Moreover, the suppressed surface defects of ZnO-K substantially improved long-term stability under air. The device using ZnO-K exhibited superior long-term air storage stability (96% retention after 90 days) compared to that using pristine ZnO (88% retention after 90 days). The ZnO-K-based device also exhibited improved photostability under air. Under continuous light illumination for 600 min, the ZnO-K-based device retained 96% of its initial PCE, whereas the pristine ZnO-based device retained only 67%.

Photosynthetic artificial organelles sustain and control ATP-dependent reactions in a protocellular system.

Inside cells, complex metabolic reactions are distributed across the modular compartments of organelles. Reactions in organelles have been recapitulated in vitro by reconstituting functional protein machineries into membrane systems. However, maintaining and controlling these reactions is challenging. Here we designed, built, and tested a switchable, light-harvesting organelle that provides both a sustainable energy source and a means of directing intravesicular reactions. An ATP (ATP) synthase and two photoconverters (plant-derived photosystem II and bacteria-derived proteorhodopsin) enable ATP synthesis. Independent optical activation of the two photoconverters allows dynamic control of ATP synthesis: red light facilitates and green light impedes ATP synthesis. We encapsulated the photosynthetic organelles in a giant vesicle to form a protocellular system and demonstrated optical control of two ATP-dependent reactions, carbon fixation and actin polymerization, with the latter altering outer vesicle morphology. Switchable photosynthetic organelles may enable the development of biomimetic vesicle systems with regulatory networks that exhibit homeostasis and complex cellular behaviors.

Manipulation of Chain Conformation for Optimum Charge-Transport Pathways in Conjugated Polymers.

A pair of different diketopyrrolopyrrole-based conjugated polymers (CPs) were designed and synthesized to investigate the effect of chain conformation on their molecular assembly. Conformation management was achieved by the incorporation of different linkers during polymerization. Through the use of computational calculations and UV-vis absorption measurements, the resulting CPs (PDPP-T and PDPP-BT) were found to exhibit partly modulated chain geometry. Grazing incident X-ray diffraction experiments with a two-dimensional detector revealed that PDPP-T having a planar chain conformation exhibited an edge-on type molecular arrangement, which evolved to a face-on type chain assembly when the planar geometry was altered to a slightly twisted one as in PDPP-BT. In addition, it was verified that the directional electric carrier mobility of CPs was critically distinguished by the distinctive chain arrangement in spite of their similar chemical structure. Concentration-dependent absorption measurements could provide an improved understanding of the assembly mechanism of CP chains: the planar conformation of PDPP-T facilitates the formation of preassembled chains in a concentrated solution and further directs the edge-on stacking, while the twisted dihedral angle along the benzothiophene in PDPP-BT prevents chain assembly, resulting in the face-on stacking. Because CP chain conformation is inevitably connected with the generation of preassembled chains, manipulating CP geometry could be an efficient tool for extracting an optimum chain assembly that is connected with the principal charge-transport pathway in CPs.

CdSe@ZnS/ZnS quantum dots loaded in polymeric micelles as a pH-triggerable targeting fluorescence imaging probe for detecting cerebral ischemic area.

High photoluminescence (PL) quantum yield (QY), photostability CdSe@ZnS/ZnS core/multishell quantum dots (CM-QDs) were first applied for bioimaging. The solubility, stability and biocompatible of the fluorescence imaging probes were constructed by self-assembly of CM-QDs and pH-responsive methoxy poly(ethylene glycol)-poly(ß-amino ester/amidoamine)-dodecylamine (mPEG-PAEA-DDA) multiblock copolymers. The resulting CM-QDs-loaded mPEG-PAEA-DDA micelles (CM-QDs-PEG-PAEA-DDA) exhibited lower cell cytotoxicity and higher fluorescence intensity than the core/shell CdSe@ZnS QDs-encapsulated mPEG-PAEA-DDA micelles (CS-QDs-PEG-PAEA-DDA). Moreover, the in vivo fluorescence imaging ability confirmed that the CM-QDs-PEG-PAEA-DDA can be employed as a pH-triggerable targeting imaging probe for detection of a rat bearing cerebral ischemia disease. Therefore, we believed that the CM-QDs-PEG-PAEA-DDA may be the next generation of fluorescence imaging probes for targeted diagnosis acidic pathological areas, using pH as a stimulus.

High-Efficiency Photovoltaic Devices using Trap-Controlled Quantum-Dot Ink prepared via Phase-Transfer Exchange.

Colloidal-quantum-dot (CQD) photovoltaic devices are promising candidates for low-cost power sources owing to their low-temperature solution processability and bandgap tunability. A power conversion efficiency (PCE) of >10% is achieved for these devices; however, there are several remaining obstacles to their commercialization, including their high energy loss due to surface trap states and the complexity of the multiple-step CQD-layer-deposition process. Herein, high-efficiency photovoltaic devices prepared with CQD-ink using a phase-transfer-exchange (PTE) method are reported. Using CQD-ink, the fabrication of active layers by single-step coating and the suppression of surface trap states are achieved simultaneously. The CQD-ink photovoltaic devices achieve much higher PCEs (10.15% with a certified PCE of 9.61%) than the control devices (7.85%) owing to improved charge drift and diffusion. Notably, the CQD-ink devices show much lower energy loss than other reported high-efficiency CQD devices. This result reveals that the PTE method is an effective strategy for controlling trap states in CQDs.

Photoresponse of CsPbBr3 and Cs4PbBr6 Perovskite Single Crystals.

High-quality and millimeter-sized perovskite single crystals of CsPbBr3 and Cs4PbBr6 were prepared in organic solvents and studied for correlation between photocurrent generation and photoluminescence (PL) emission. The CsPbBr3 crystals, which have a 3D perovskite structure, showed a highly sensitive photoresponse and poor PL signal. In contrast, Cs4PbBr6 crystals, which have a 0D perovskite structure, exhibited more than 1 order of magnitude higher PL intensity than CsPbBr3, which generated an ultralow photoresponse under illumination. Their contrasting optoelectrical characteristics were attributed to different exciton binding energies, induced by coordination geometry of the [PbBr6]4- octahedron sublattices. This work correlated the local structures of lead in the primitive perovskite and its derivatives to PL spectra as well as photoconductivity.

Investigation into the Advantages of Pure Perovskite Film without PbI2 for High Performance Solar Cell.

In CH3NH3PbI3-based high efficiency perovskite solar cells (PSCs), tiny amount of PbI2 impurity was often found with the perovskite crystal. However, for two-step solution process-based perovskite films, most of findings have been based on the films having different morphologies between with and without PbI2. This was mainly due to the inferior morphology of pure perovskite film without PbI2, inevitably produced when the remaining PbI2 forced to be converted to perovskite, so advantages of pure perovskite photoactive layer without PbI2 impurity have been overlooked. In this work, we designed a printing-based two-step process, which could not only generate pure perovskite crystal without PbI2, but also provide uniform and full surface coverage perovskite film, of which nanoscale morphology was comparable to that prepared by conventional two-step solution process having residual PbI2. Our results showed that, in two-step solution process-based PSC, pure perovskite had better photon absorption and longer carrier lifetime, leading to superior photocurrent generation with higher power conversion efficiency. Furthermore, this process was further applicable to prepare mixed phase pure perovskite crystal without PbI2 impurity, and we showed that the additional merits such as extended absorption to longer wavelength, increased carrier lifetime and reduced carrier recombination could be secured.

Fabrication of Efficient Formamidinium Tin Iodide Perovskite Solar Cells through SnF2-Pyrazine Complex.

To fabricate efficient formamidinium tin iodide (FASnI3) perovskite solar cells (PSCs), it is essential to deposit uniform and dense perovskite layers and reduce Sn(4+) content. Here we used solvent-engineering and nonsolvent dripping process with SnF2 as an inhibitor of Sn(4+). However, excess SnF2 induces phase separation on the surface of the perovskite film. In this work, we report the homogeneous dispersion of SnF2 via the formation of the SnF2-pyrazine complex. Consequently, we fabricated FASnI3 PSCs with high reproducibility, achieving a high power conversion efficiency of 4.8%. Furthermore, the encapsulated device showed a stable performance for over 100 days, maintaining 98% of its initial efficiency.

The nucleolar GTPase nucleostemin-like 1 plays a role in plant growth and senescence by modulating ribosome biogenesis.

Nucleostemin is a nucleolar GTP-binding protein that is involved in stem cell proliferation, embryonic development, and ribosome biogenesis in mammals. Plant nucleostemin-like 1 (NSN1) plays a role in embryogenesis, and apical and floral meristem development. In this study, a nucleolar function of NSN1 in the regulation of ribosome biogenesis was identified. Green fluorescent protein (GFP)-fused NSN1 localized to the nucleolus, which was primarily determined by its N-terminal domain. Recombinant NSN1 and its N-terminal domain (NSN1-N) bound to RNA in vitro. Recombinant NSN1 expressed GTPase activity in vitro. NSN1 silencing in Arabidopsis thaliana and Nicotiana benthamiana led to growth retardation and premature senescence. NSN1 interacted with Pescadillo and EBNA1 binding protein 2 (EBP2), which are nucleolar proteins involved in ribosome biogenesis, and with several ribosomal proteins. NSN1, NSN1-N, and EBP2 co-fractionated primarily with the 60S ribosomal large subunit in vivo. Depletion of NSN1 delayed 25S rRNA maturation and biogenesis of the 60S ribosome subunit, and repressed global translation. NSN1-deficient plants exhibited premature leaf senescence, excessive accumulation of reactive oxygen species, and senescence-related gene expression. Taken together, these results suggest that NSN1 plays a crucial role in plant growth and senescence by modulating ribosome biogenesis.

Efficient CH3 NH3 PbI3 Perovskite Solar Cells Employing Nanostructured p-Type NiO Electrode Formed by a Pulsed Laser Deposition.

Highly transparent and nanostructured nickel oxide (NiO) films through pulsed laser deposition are introduced for efficient CH3 NH3 PbI3 perovskite solar cells. The (111)-oriented nanostructured NiO film plays a key role in extracting holes and preventing electron leakage as hole transporting material. The champion device exhibits a power conversion efficiency of 17.3% with a very high fill factor of 0.813.

Understanding the role of the dye/oxide interface via SnO2-based MK-2 dye-sensitized solar cells.

To understand the role of the dye/oxide interface, a model system using a nanocrystalline SnO2 and 3-hexyl thiophene based MK-2 dye is proposed. A thin interfacial TiO2 blocking layer (IBL) is introduced in between SnO2 and MK-2 and its effects on photocurrent-voltage, electron transport-recombination, and density of states (DOS) are systematically investigated. Compared to the bare SnO2 film, the insertion of IBL leads to a 14-fold improvement in the power conversion efficiency (PCE) despite little change in the dye adsorption amount, which is due to the 7-fold and 2-fold increase in the photocurrent density and voltage, respectively. The charge collection efficiency is substantially improved from 38% to 96% mainly due to the increase in the electron lifetime. The IBL is also found to enhance the dye regeneration efficiency as confirmed by the 15-fold faster dye bleaching recovery dynamics. The recombination resistance increases and the DOS decreases after surface modification of SnO2, which is responsible for the doubly increased voltage. This study suggests that the interfacial layer between the oxide and the dye plays a crucial role in retarding recombination, improving charge collection efficiency, increasing diffusion length, accelerating dye regeneration and narrowing the density of states.

Direct Low-Temperature Growth of Single-Crystalline Anatase TiO2 Nanorod Arrays on Transparent Conducting Oxide Substrates for Use in PbS Quantum-Dot Solar Cells.

We report on the direct growth of anatase TiO2 nanorod arrays (A-NRs) on transparent conducting oxide (TCO) substrates that can be directly applied to various photovoltaic devices via a seed layer mediated epitaxial growth using a facile low-temperature hydrothermal method. We found that the crystallinity of the seed layer and the addition of an amine functional group play crucial roles in the A-NR growth process. The A-NRs exhibit a pure anatase phase with a high crystallinity and preferred growth orientation in the [001] direction. Importantly, for depleted heterojunction solar cells (TiO2/PbS), the A-NRs improve both electron transport and injection properties, thereby largely increasing the short-circuit current density and doubling their efficiency compared to TiO2 nanoparticle-based solar cells.