Probing twisted intramolecular charge transfer of pyrene derivatives as organic emitters in OLEDs.

Intramolecular charge transfer (ICT) plays a critical role in determining the photophysical properties of organic molecules, including their luminescence efficiencies. Twisted intramolecular charge transfer (TICT) is a process in which structural change accompanies ICT. Herein, we used time-resolved spectroscopy to study TICT in pyrene derivatives that are promising blue organic light emitting diode (OLED) emitter candidates; these derivatives show strong solvent-dependent charge-transfer (CT) behavior with unique fluorescence properties, increased fluorescence intensity in polar solvent. Slight structural changes that do not affect excited state dynamics were observed in nonpolar solvents, while polar solvents were found to affect excited state dynamics and CT characteristics, which affect their unusual fluorescence behavior. The TICT behavior of these pyrene derivatives can be modulated through structural modification. Our study provides valuable guidelines for the control of optical properties, including the luminescence efficiencies of OLED emitters that show TICT characteristics.

Classification of the Sidewalk Condition Using Self-Supervised Transfer Learning for Wheelchair Safety Driving.

The demand for wheelchairs has increased recently as the population of the elderly and patients with disorders increases. However, society still pays less attention to infrastructure that can threaten the wheelchair user, such as sidewalks with cracks/potholes. Although various studies have been proposed to recognize such challenges, they mainly depend on RGB images or IMU sensors, which are sensitive to outdoor conditions such as low illumination, bad weather, and unavoidable vibrations, resulting in unsatisfactory and unstable performance. In this paper, we introduce a novel system based on various convolutional neural networks (CNNs) to automatically classify the condition of sidewalks using images captured with depth and infrared modalities. Moreover, we compare the performance of training CNNs from scratch and the transfer learning approach, where the weights learned from the natural image domain (e.g., ImageNet) are fine-tuned to the depth and infrared image domain. In particular, we propose applying the ResNet-152 model pre-trained with self-supervised learning during transfer learning to leverage better image representations. Performance evaluation on the classification of the sidewalk condition was conducted with 100% and 10% of training data. The experimental results validate the effectiveness and feasibility of the proposed approach and bring future research directions.

Increasing the Energy Gap between Band-Edge and Trap States Slows Down Picosecond Carrier Trapping in Highly Luminescent InP/ZnSe/ZnS Quantum Dots.

Non-toxic InP-based nanocrystals have been developed for promising candidates for commercial optoelectronic applications and they still require further improvement on photophysical properties, compared to Cd-based quantum dots (QDs), for better device efficiency and long-term stability. It is, therefore, essential to understand the precise mechanism of carrier trapping even in the state-of-the-art InP-based QD with near-unity luminescence. Here, it is shown that using time-resolved spectroscopic measurements of systematically size-controlled InP/ZnSe/ZnS core/shell/shell QDs with the quantum yield close to one, carrier trapping decreases with increasing the energy difference between band-edge and trap states, indicating that the process follows the energy gap law, well known in molecular photochemistry for nonradiative internal conversion between two electronic states. Similar to the molecular view of the energy gap law, it is found that the energy gap between the band-edge and trap states is closely associated with ZnSe phonons that assist carrier trapping into defects in highly luminescent InP/ZnSe/ZnS QDs. These findings represent a striking departure from the generally accepted view of carrier trapping mechanism in QDs in the Marcus normal region, providing a step forward understanding how excitons in nanocrystals interact with traps, and offering valuable guidance for making highly efficient and stable InP-based QDs.

Hidden Charge Order in an Iron Oxide Square-Lattice Compound.

Since the discovery of charge disproportionation in the FeO_{2} square-lattice compound Sr_{3}Fe_{2}O_{7} by Mössbauer spectroscopy more than fifty years ago, the spatial ordering pattern of the disproportionated charges has remained "hidden" to conventional diffraction probes, despite numerous x-ray and neutron scattering studies. We have used neutron Larmor diffraction and Fe K-edge resonant x-ray scattering to demonstrate checkerboard charge order in the FeO_{2} planes that vanishes at a sharp second-order phase transition upon heating above 332 K. Stacking disorder of the checkerboard pattern due to frustrated interlayer interactions broadens the corresponding superstructure reflections and greatly reduces their amplitude, thus explaining the difficulty of detecting them by conventional probes. We discuss the implications of these findings for research on "hidden order" in other materials.

Gaze in the Dark: Gaze Estimation in a Low-Light Environment with Generative Adversarial Networks.

In smart interactive environments, such as digital museums or digital exhibition halls, it is important to accurately understand the user's intent to ensure successful and natural interaction with the exhibition. In the context of predicting user intent, gaze estimation technology has been considered one of the most effective indicators among recently developed interaction techniques (e.g., face orientation estimation, body tracking, and gesture recognition). Previous gaze estimation techniques, however, are known to be effective only in a controlled lab environment under normal lighting conditions. In this study, we propose a novel deep learning-based approach to achieve a successful gaze estimation under various low-light conditions, which is anticipated to be more practical for smart interaction scenarios. The proposed approach utilizes a generative adversarial network (GAN) to enhance users' eye images captured under low-light conditions, thereby restoring missing information for gaze estimation. Afterward, the GAN-recovered images are fed into the convolutional neural network architecture as input data to estimate the direction of the user gaze. Our experimental results on the modified MPIIGaze dataset demonstrate that the proposed approach achieves an average performance improvement of 4.53%-8.9% under low and dark light conditions, which is a promising step toward further research.

Green-light-selective organic photodiodes for full-color imaging.

In this work, organic photodiodes (OPDs) based on two newly synthesized p-type dipolar small molecules are reported for application to green-light-selective OPDs. In order to reduce the blue-color absorption induced by the use of C60 as the n-type material in a bulk heterojunction (BHJ), the electron donor:electron acceptor composition ratio is tuned in the BHJ. With this light manipulation approach, the blue-wavelength external quantum efficiency (EQE) is minimized to 18% after reducing the C60 concentration in the center part of the BHJ. The two p-type molecules get a cyanine-like character with intense and sharp absorption in the green color by adjusting the strength of their donating and accepting parts and by choosing a selenophene unit as a π-linker. When combined to C60, the green-wavelength EQE reaches 70% in a complete device composed of two transparent electrodes. Finally, the optical simulation shows the good color-balance performance of hybrid full-color image sensor without an additional filter by using the developed green OPD as the top-layer in stacked device architecture.

BPA-toxicity via superoxide anion overload and a deficit in ß-catenin signaling in human bone mesenchymal stem cells.

Bisphenol A (BPA), used in the manufacture of products based on polycarbonate plastics and epoxy resins, is well known as an endocrine-disrupting monomer. In the current study, BPA increased cytotoxicity in hBMSCs in a dose- and time-dependent manner, concomitantly with increased lipid peroxidation. Increased cell death in BPA-treated cells was markedly blocked by pretreatment with the superoxide dismutase mimetic MnTBAP and MnTMPyP, but not by catalase, glutathione, the glutathione peroxidase mimetic ebselen, the NOS inhibitor NAME, or the xanthine oxidase inhibitor allopurinol. Furthermore, the decline in nuclear ß-catenin and cyclin D1 levels in hBMSCs exposed to BPA was reversed by MnTBAP treatment. Finally, treatment of hBMSCs with the GSK3ß inhibitor LiCl2 increased nuclear ß-catenin levels and significantly attenuated cytotoxicity compared with BPA treatment. Our current results in hBMSCs exposed to BPA suggest that BPA causes a disturbance in ß-catenin signaling via a superoxide anion overload. © 2016 The Authors Environmental Toxicology Published by Wiley Periodicals, Inc. Environ Toxicol 32: 344-352, 2017.

Study on the disparate transition behaviors of the electrical/physical properties in PEDOT:PSS film depending on solvent species under a follow-up solution-treatment process.

In most solution-processed organic devices, a poly(3,4-ethylenedioxythiophene) (PEDOT) polymerized with poly(4-styrenesulfonate) (PSS) film is inevitably affected by various conditions during the subsequent solution-coating processes. To investigate the effects of direct solvent exposure on the properties of PEDOT polymerized with PSS (PEDOT:PSS) films, photoemission spectroscopy-based analytical methods were used before and after solvent-coating processes. Our results clearly indicate that PEDOT: PSS films undergo a different transition mechanism depending on the solubility of the solvent in water. The water-miscible solvents induce the solvation of hydrophilic PSS chains. As a result, this process allows the solvent to diffuse into the PEDOT: PSS film, and a conformational change between PEDOT and PSS occurs. On the other hand, the water-immiscible organic solvents cause the partial adsorption of solvent molecules at the PE surface, which leads to changes in the surface properties, including work function. Based on our finding, we demonstrate that the energy-level alignments at the organic semiconductor/electrode interface for the PEDOT: PSS films can be controlled by simple solvent treatments.

The prediction of hole mobility in organic semiconductors and its calibration based on the grain-boundary effect.

A new reliable computational model to predict the hole mobility of poly-crystalline organic semiconductors in thin films was developed. Site energy differences and transfer integrals in crystalline morphologies of organic molecules were obtained from quantum chemical calculations, in which periodic boundary conditions were efficiently applied to capture the interactions with the surrounding molecules in the crystalline organic layer. Then the parameters were employed in kinetic Monte Carlo (kMC) simulations to estimate the carrier mobility. Carrier transport in multiple directions has been considered in the kMC simulation to mimic poly-crystalline characteristics under thin-film conditions. Furthermore, the calculated mobility was corrected using a calibration equation based on microscopy images of the thin films to take the effect of grain boundaries into account. As a result, good agreement was observed between the predicted and measured hole mobility values for 21 molecular species: the coefficient of determination (R(2)) was estimated to be 0.83 and the mean absolute error was 1.32 cm(2) V(-1) s(-1). This numerical approach can be applied to any molecules for which crystal structures are available and will provide a rapid and precise way of predicting device performance.

Simultaneous measurements of temporal evolutions of the voltage and the current on the load of the Seoul National University X-pinch device using the optics-based systems.

Optics-based measurement systems have been developed to measure the voltage and the current on a load of the Seoul National University X-pinch device [Ryu et al., Rev. Sci. Instrum. 92, 053533 (2021)]. A lithium niobate crystal that changes the polarization state of the propagating laser beam due to the Pockels effect induced by the electric field across the crystal, thus capable of measuring the voltage, is located next to the load. For the current measurement, an optic fiber is wound around the load to detect the change in the polarization state of the propagating laser beam due to the Faraday rotation induced by the magnetic field. As both voltage and current measurement systems utilize optical effects, the sensors, i.e., the lithium niobate crystal and the optic fiber, do not require any electrical grounds, in contrast to circuit-based probes, such as voltage dividers or Rogowski grooves. This facilitates an easy access to shield other required electronic devices, such as lasers and photodetectors, from the electromagnetic interference generated by the X-pinch power system. In addition, the sensors can be placed in close proximity to the load with fewer concerns on the electrical insulation. Temporal evolutions of the simultaneously measured voltage and current on the load of the X-pinch are successfully obtained and discussed.

Effect of trifluoroacetic acid on InP/ZnSe/ZnS quantum dots: mimicking the surface trap and their effects on the photophysical properties.

Understanding the precise effects of defects on the photophysical properties of quantum dots (QDs) is essential to their development with near-unity luminescence. Because of the complicated nature of defects in QDs, the origins and detailed roles of the defects still remain rarely understood. In this regard, we used detailed chemical analysis to investigate the effect of surface defects on the optical properties of InP/ZnSe/ZnS QDs by introducing shell defects through controlled trifluoroacetic acid (TFA) etching. TFA treatment on the InP/ZnSe/ZnS QDs partially removed the ZnS shell as well as ligands and reduced the quantum yield by generating energetically deep surface traps. The surface defects of QDs by TFA cause charged trap sites inducing an Auger recombination process with a rate of ca. 200 ps. Based on these results, we proposed possible trap-assisted non-radiative decay pathways between the band-edge state and surface deep traps in InP/ZnSe/ZnS QDs.

Direct identification of interfacial degradation in blue OLEDs using nanoscale chemical depth profiling.

Understanding the degradation mechanism of organic light-emitting diodes (OLED) is essential to improve device performance and stability. OLED failure, if not process-related, arises mostly from chemical instability. However, the challenges of sampling from nanoscale organic layers and interfaces with enough analytical information has hampered identification of degradation products and mechanisms. Here, we present a high-resolution diagnostic method of OLED degradation using an Orbitrap mass spectrometer equipped with a gas cluster ion beam to gently desorb nanometre levels of materials, providing unambiguous molecular information with 7-nm depth resolution. We chemically depth profile and analyse blue phosphorescent and thermally-activated delayed fluorescent (TADF) OLED devices at different degradation levels. For OLED devices with short operational lifetimes, dominant chemical degradation mainly relate to oxygen loss of molecules that occur at the interface between emission and electron transport layers (EML/ETL) where exciton distribution is maximised, confirmed by emission zone measurements. We also show approximately one order of magnitude increase in lifetime of devices with slightly modified host materials, which present minimal EML/ETL interfacial degradation and show the method can provide insight for future material and device architecture development.

High-energy and durable lithium metal batteries using garnet-type solid electrolytes with tailored lithium-metal compatibility.

Lithium metal batteries using solid electrolytes are considered to be the next-generation lithium batteries due to their enhanced energy density and safety. However, interfacial instabilities between Li-metal and solid electrolytes limit their implementation in practical batteries. Herein, Li-metal batteries using tailored garnet-type Li7-xLa3-aZr2-bO12 (LLZO) solid electrolytes is reported, which shows remarkable stability and energy density, meeting the lifespan requirements of commercial applications. We demonstrate that the compatibility between LLZO and lithium metal is crucial for long-term stability, which is accomplished by bulk dopant regulating and dopant-specific interfacial treatment using protonation/etching. An all-solid-state with 5 mAh cm-2 cathode delivers a cumulative capacity of over 4000 mAh cm-2 at 3 mA cm-2, which to the best of our knowledge, is the highest cycling parameter reported for Li-metal batteries with LLZOs. These findings are expected to promote the development of solid-state Li-metal batteries by highlighting the efficacy of the coupled bulk and interface doping of solid electrolytes.

Radial profile measurement with an improved 1 kHz Thomson scattering system on Versatile Experiment Spherical Torus.

A Thomson scattering (TS) system has been utilized to measure the electron temperature and density of the core region of Versatile Experiment Spherical Torus (VEST). Recently, the laser injection system is successfully upgraded adopting the burst laser with the repetition rate of 1 kHz and the energy of 2 J. Furthermore, improved collection optics with additional polychromators and a 32-channel fast digitizer are prepared to observe the fast time evolution of radial profiles. This improvement is essential to study fast phenomena such as internal reconnection event (IRE). We increase the TS signal and reduce the stray light by introducing new filters having better optical properties such as high optical density at 1064 nm, transmission, and reflectance. Moreover, the optimum reverse bias voltages are newly set to make the system operational independent of the background radiation. As a result, 1 kHz radial profiles of the core electron temperature and density are measured for the first time, showing characteristics of IREs in VEST.

Unveiling the Origin of Robust Ferroelectricity in Sub-2 nm Hafnium Zirconium Oxide Films.

HfO2-based ferroelectrics are highly expected to lead the new paradigm of nanoelectronic devices owing to their unexpected ability to enhance ferroelectricity in the ultimate thickness scaling limit (≤2 nm). However, an understanding of its physical origin remains uncertain because its direct microstructural and chemical characterization in such a thickness regime is extremely challenging. Herein, we solve the mystery for the continuous retention of high ferroelectricity in an ultrathin hafnium zirconium oxide (HZO) film (∼2 nm) by unveiling the evolution of microstructures and crystallographic orientations using a combination of state-of-the-art structural analysis techniques beyond analytical limits and theoretical approaches. We demonstrate that the enhancement of ferroelectricity in ultrathin HZO films originates from textured grains with a preferred orientation along an unusual out-of-plane direction of (112). In principle, (112)-oriented grains can exhibit 62% greater net polarization than the randomly oriented grains observed in thicker samples (>4 nm). Our first-principles calculations prove that the hydroxyl adsorption during the deposition process can significantly reduce the surface energy of (112)-oriented films, thereby stabilizing the high-index facet of (112). This work provides new insights into the ultimate scaling of HfO2-based ferroelectrics, which may facilitate the design of future extremely small-scale logic and memory devices.

Risk factors of postoperative major adverse cardiac events after radical cystectomy: implication of diastolic dysfunction.

Radical cystectomy, which is a standard treatment of muscle invasive and high-grade non-invasive bladder tumour, is accompanied with high rates of postoperative complications including major adverse cardiac events (MACE). Diastolic dysfunction is associated with postoperative complications. We evaluated perioperative risk factors including diastolic dysfunction related with MACE within 6 months after radical cystectomy. The 546 patients who underwent elective radical cystectomy were included. Diastolic dysfunction was defined as early transmitral flow velocity (E)/early diastolic mitral annulus velocity (e') > 15. Logistic regression analysis, Kaplan-Meier survival analysis and log-rank test were performed. MACE within 6 months after radical cystectomy developed in 43 (7.9%) patients. MACE was related with female (odds ratio 2.546, 95% confidence interval 1.166-5.557, P = 0.019) and diastolic dysfunction (odds ratio 3.077, 95% confidence interval 1.147-8.252, P = 0.026). The 6-month mortality were significantly higher in the MACE group, and hospital stay and intensive care unit stay were significantly longer in the MACE group compared to the non-MACE group. Accordingly, preoperative diastolic dysfunction (E/e' > 15) was related with postoperative MACE and MACE was related with 6-month survival after radical cystectomy. These results suggest that preoperative diastolic dysfunction can provide useful information on postoperative complications.

Dissociation of intermolecular disulfide bonds in P22 tailspike protein intermediates in the presence of SDS.

Each chain of the native trimeric P22 tailspike protein has eight cysteines that are reduced and buried in its hydrophobic core. However, disulfide bonds have been observed in the folding pathway and they are believed to play a critical role in the registration of the three chains. Interestingly, in the presence of sodium dodecyl sulfate (SDS) only monomeric chains, rather than disulfide-linked oligomers, have been observed from a mixture of folding intermediates. Here we show that when the oligomeric folding intermediates were separated from the monomer by native gel electrophoresis, the reduction of intermolecular disulfide bonds did not occur in the subsequent second-dimension SDS-gel electrophoresis. This result suggests that when tailspike monomer is present in free solution with SDS, the partially unfolded tailspike monomer can facilitate the reduction of disulfide bonds in the tailspike oligomers.

Mutational analysis of promoters of mismatch repair genes hMSH2 and hMLH1 in hereditary nonpolyposis colorectal cancer and early onset colorectal cancer patients: identification of three novel germ-line mutations in promoter of the hMSH2 gene.

The human DNA mismatch repair genes hMSH2 and hMLH1 are responsible for the development of hereditary nonpolyposis colorectal cancer (HNPCC). Although genetic alteration of the coding region of hMSH2 and hMLH1 has been well investigated in HNPCC patients, the regulatory regions of these genes have been poorly investigated, though recent studies have defined and characterized the core promoter regions of hMSH2 and hMLH1. Therefore, to investigate the presence of germ-line mutations, we screened the core promoter regions of hMSH2 and hMLH1 from 157 nonmalignant control individuals, 40 cases of HNPCC, 56 suspected HNPCC cases, and 45 sporadic early onset colorectal cancer patients. Three novel germ-line mutations of the hMSH2 promoter were identified in two suspected HNPCC cases and one sporadic early onset colorectal cancer patient but not in the 157 nonmalignant controls, namely, an A insertion at position -80, a G-to-A transition at position -190, and a G-to-C transversion at position -225. Tumors from patients containing the promoter mutations displayed microsatellite instability. The A insertion at -80 is within a sequence homologous to the consensus sequence for E1AF and very close to the major transcription start point. Luciferase assay demonstrated that the -80A insertion and the -190A allele decreased the transcriptional efficiency by 82 and 77%, respectively, and the -225C allele increased the transcriptional efficiency by 466%. The -80A insertion allele was detected only in affected members within the family and showed novel transcription factor binding ability. Furthermore, the loss of single nucleotide polymorphism allelic expression was identified in blood of the patient containing the -80A insertion. Our results indicate that mutations in the promoter region of hMSH2 have a limited role in development of suspected HNPCC and sporadic early onset colorectal cancer.

Intermolecular Markovnikov-Selective Hydroacylation of Olefins Catalyzed by a Cationic Ruthenium-Hydride Complex.

The cationic Ru-H complex was found to be an effective catalyst for the intermolecular hydroacylation of aryl-substituted olefins with aldehydes to form branched ketone products. The preliminary kinetic and spectroscopic studies elucidated a ruthenium-acyl complex as the key intermediate species. The catalytic method directly afforded branched ketone products in a highly regioselective manner while tolerating a number of heteroatom functional groups.