Ultraviolet light blocking optically clear adhesives for foldable displays via highly efficient visible-light curing.

In developing an organic light-emitting diode (OLED) panel for a foldable smartphone (specifically, a color filter on encapsulation) aimed at reducing power consumption, the use of a new optically clear adhesive (OCA) that blocks UV light was crucial. However, the incorporation of a UV-blocking agent within the OCA presented a challenge, as it restricted the traditional UV-curing methods commonly used in the manufacturing process. Although a visible-light curing technique for producing UV-blocking OCA was proposed, its slow curing speed posed a barrier to commercialization. Our study introduces a highly efficient photo-initiating system (PIS) for the rapid production of UV-blocking OCAs utilizing visible light. We have carefully selected the photocatalyst (PC) to minimize electron and energy transfer to UV-blocking agents and have chosen co-initiators that allow for faster electron transfer and more rapid PC regeneration compared to previously established amine-based co-initiators. This advancement enabled a tenfold increase in the production speed of UV-blocking OCAs, while maintaining their essential protective, transparent, and flexible properties. When applied to OLED devices, this OCA demonstrated UV protection, suggesting its potential for broader application in the safeguarding of various smart devices.

Visible-Light-Driven Rapid 3D Printing of Photoresponsive Resins for Optically Clear Multifunctional 3D Objects.

Light-driven 3D printing is gaining significant attention for its unparalleled build speed and high-resolution in additive manufacturing. However, extending vat photopolymerization to multifunctional, photoresponsive materials poses challenges, such as light attenuation and interference between the photocatalysts (PCs) and photoactive moieties. This study introduces novel visible-light-driven acrylic resins that enable rapid, high-resolution photoactive 3D printing. The synergistic combination of a cyanine-based PC, borate, and iodonium coinitiators (HNu 254) achieves an excellent printing rate and feature resolution under low-intensity, red light exposure. The incorporation of novel hexaarylbiimidazole (HABI) crosslinkers allows for spatially-resolved photoactivation upon exposure to violet/blue light. Furthermore, a photobleaching mechanism inhibited by HNu 254 during the photopolymerization process results in the production of optically-clear 3D printed objects. Real-time Fourier transform infrared spectroscopy validates the rapid photopolymerization of the HABI-containing acrylic resin, whereas mechanistic evaluations reveal the underlying dynamics that are responsible for the rapid photopolymerization rate, wavelength-orthogonal photoactivation, and observed photobleaching phenomenon. Ultimately, this visible-light-based printing method demonstrates: (i) rapid printing rate of 22.5 mm h-1, (ii) excellent feature resolution (≈20 µm), and (iii) production of optically clear object with self-healing capability and spatially controlled cleavage. This study serves as a roadmap for developing next-generation "smart" 3D printing technologies.

Characterization of the Reversible Intersystem Crossing Dynamics of Organic Photocatalysts Using Transient Absorption Spectroscopy and Time-Resolved Fluorescence Spectroscopy.

Thermally activated delayed fluorescence (TADF) emitters are molecules of interest as homogeneous organic photocatalysts (OPCs) for photoredox chemistry. Here, three classes of OPC candidates are studied in dichloromethane (DCM) or N,N-dimethylformamide (DMF) solutions, using transient absorption spectroscopy and time-resolved fluorescence spectroscopy. These OPCs are benzophenones with either carbazole (2Cz-BP and 2tCz-BP) or phenoxazine/phenothiazine (2PXZ-BP and 2PTZ-BP) appended groups and the dicyanobenzene derivative 4DP-IPN. Dual lifetimes of the S1 state populations are observed, consistent with reverse intersystem crossing (RISC) and TADF emission. Example fluorescence lifetimes in DCM are (5.18 ± 0.01) ns and (6.22 ± 1.27) µs for 2Cz-BP, (1.38 ± 0.01) ns and (0.32 ± 0.01) µs for 2PXZ-BP, and (2.97 ± 0.01) ns and (62.0 ± 5.8) µs for 4DP-IPN. From ground state bleach recoveries and time-correlated single photon counting measurements, triplet quantum yields in DCM are estimated to be 0.62 ± 0.16, 0.04 ± 0.01, and 0.83 ± 0.02 for 2Cz-BP, 2PXZ-BP, and 4DP-IPN, respectively. 4DP-IPN displays similar photophysical behavior to the previously studied OPC 4Cz-IPN. Independent of the choice of solvent, 4DP-IPN, 2Cz-BP, and 2tCz-BP are shown to be TADF emitters, whereas emission by 2PXZ-BP and 2PTZ-BP depends on the molecular environment, with TADF emission enhanced in aggregates compared to monomers. Behavior of this type is representative of aggregation-induced emission luminogens (AIEgens).

Formation and degradation of strongly reducing cyanoarene-based radical anions towards efficient radical anion-mediated photoredox catalysis.

Cyanoarene-based photocatalysts (PCs) have attracted significant interest owing to their superior catalytic performance for radical anion mediated photoredox catalysis. However, the factors affecting the formation and degradation of cyanoarene-based PC radical anion (PC•‒) are still insufficiently understood. Herein, we therefore investigate the formation and degradation of cyanoarene-based PC•‒ under widely-used photoredox-mediated reaction conditions. By screening various cyanoarene-based PCs, we elucidate strategies to efficiently generate PC•‒ with adequate excited-state reduction potentials (Ered*) via supra-efficient generation of long-lived triplet excited states (T1). To thoroughly investigate the behavior of PC•‒ in actual photoredox-mediated reactions, a reductive dehalogenation is carried out as a model reaction and identified the dominant photodegradation pathways of the PC•‒. Dehalogenation and photodegradation of PC•‒ are coexistent depending on the rate of electron transfer (ET) to the substrate and the photodegradation strongly depends on the electronic and steric properties of the PCs. Based on the understanding of both the formation and photodegradation of PC•‒, we demonstrate that the efficient generation of highly reducing PC•‒ allows for the highly efficient photoredox catalyzed dehalogenation of aryl/alkyl halides at a PC loading as low as 0.001 mol% with a high oxygen tolerance. The present work provides new insights into the reactions of cyanoarene-based PC•‒ in photoredox-mediated reactions.

Visible-Light-Curable Acrylic Resins toward UV-Light-Blocking Adhesives for Foldable Displays.

Current technological advances in the organic light-emitting diode panel design of foldable smartphones demand advanced adhesives with UV-blocking abilities, beyond their conventional roles of bonding objects and relieving deformation stress. However, optically clear adhesives (OCAs) with UV-blocking ability cannot be prepared using conventional UV-curing methods relying on a photoinitiator. Herein, a new acrylic resin that can be efficiently cured using visible light without oxygen removal is presented, which may be used to develop UV-blocking OCAs for use in current flexible displays. A novel photocatalyst and a specific combination of additives facilitate sufficiently rapid curing under visible light in the presence of UV-absorbers. Only a very small amount of the highly active photocatalyst is required to prepare UV-blocking OCA films with very high transparency in the visible region. Using this system, a UV-blocking OCA that nearly meets the specifications of an OCA used in commercialized foldable smartphones is realized. This technology can also be utilized in other applications that require highly efficient visible light curing, such as optically clear resins, dental resins, and 3D/4D-printable materials.

Case report: Application of three-dimensional technologies for surgical treatment of portosystemic shunt with segmental caudal vena cava aplasia in two dogs.

This case report describes the application of three-dimensional (3D) technologies for the surgical treatment of portosystemic shunt (PSS) with segmental caudal vena cava (CVC) aplasia. Two client-owned dogs were diagnosed with PSS along with segmental CVC aplasia using computed tomography. Through 3D volume and surface rendering, the vascular anatomic anomaly of each patient was identified in detail. A patient-specific 3D vascular model was used for preoperative planning. According to the plan established based on the 3D rendered image and printed model, shunt occlusion was performed using cellophane banding in the first case. An ameroid constrictor was used in the second case. Both patients showed good recovery without any clinical symptoms or complications. The use of 3D technologies in small animals has many advantages, and its use in vascular surgery, as in these cases, is also a therapeutic option worth considering.

A Water-Soluble Organic Photocatalyst Discovered for Highly Efficient Additive-Free Visible-Light-Driven Grafting of Polymers from Proteins at Ambient and Aqueous Environments.

Since the pioneering discovery of a protein bound to poly(ethylene glycol), the utility of protein-polymer conjugates (PPCs) is rapidly expanding to currently emerging applications. Photoinduced energy/electron-transfer reversible addition-fragmentation chain-transfer (PET-RAFT) polymerization is a very promising method to prepare structurally well-defined PPCs, as it eliminates high-cost and time-consuming deoxygenation processes due to its oxygen tolerance. However, the oxygen-tolerance behavior of PET-RAFT polymerization is not well-investigated in aqueous environments, and thereby the preparation of PPCs using PET-RAFT polymerization needs a substantial amount of sacrificial reducing agents or inert-gas purging processes. Herein a novel water-soluble and biocompatible organic photocatalyst (PC) is reported, which enables visible-light-driven additive-free "grafting-from" polymerizations of a protein in ambient and aqueous environments. Interestingly, the developed PC shows unconventional "oxygen-acceleration" behavior for a variety of acrylic and acrylamide monomers in aqueous conditions without any additives, which are apparently distinct from previously reported systems. With such a PC, "grafting-from" polymerizations are successfully performed from protein in ambient buffer conditions under green light-emitting diode (LED) irradiation, which result in various PPCs that have neutral, anionic, cationic, and zwitterionic polyacrylates, and polyacrylamides. It is believed that this PC will be widely employed for a variety of photocatalysis processes in aqueous environments, including the living cell system.

Monitoring the vertical distribution of HABs using hyperspectral imagery and deep learning models.

Remote sensing techniques have been applied to monitor the spatiotemporal variation of harmful algal blooms (HABs) in many inland waters. However, these studies have been limited to monitor the vertical distribution of HABs due to the optical complexity of inland water. Therefore, this study applied a deep neural network model to monitor the vertical distribution of Chlorophyll-a (Chl-a), phycocyanin (PC), and turbidity (Turb) using drone-borne hyperspectral imagery, in-situ measurement, and meteoroidal data. The pigment concentrations were measured between depths of 0 m and 5.0 m with 0.05 m intervals. Here, four state-of-the-art data-driven model structures (ResNet-18, ResNet-101, GoogLeNet, and Inception v3) were adopted for estimating the vertical distributions of the harmful algal pigments. Among the four models, the ResNet-18 model showed the best performance, with an R2 value of 0.70. In addition, Gradient-weighted Class Activation Mapping (Grad-CAM) substantially provided informative reflectance band ranges near 490 nm and 620 nm in the hyperspectral image for the vertical estimation of pigments. Therefore, this study demonstrated that the explainable deep learning model with drone-borne hyperspectral images has the potential to estimate Chl-a, PC, and Turb vertical distributions and to show influential features that contribute to describing the vertical profile phenomena.

Visible-Light-Curable Solvent-Free Acrylic Pressure-Sensitive Adhesives via Photoredox-Mediated Radical Polymerization.

Owing to their excellent properties, such as transparency, resistance to oxidation, and high adhesivity, acrylic pressure-sensitive adhesives (PSAs) are widely used. Recently, solvent-free acrylic PSAs, which are typically prepared via photopolymerization, have attracted increasing attention because of the current strict environmental regulations. UV light is commonly used as an excitation source for photopolymerization, whereas visible light, which is safer for humans, is rarely utilized. In this study, we prepared solvent-free acrylic PSAs via visible light-driven photoredox-mediated radical polymerization. Three α-haloesters were used as additives to overcome critical shortcomings, such as the previously reported low film curing rate and poor transparency observed during additive-free photocatalytic polymerization. The film curing rate was greatly increased in the presence of α-haloesters, which lowered the photocatalyst loadings and, hence, improved the film transparency. These results confirmed that our method could be widely used to prepare general-purpose solvent-free PSAs-in particular, optically clear adhesives for electronics.

Evaluating the uncertainty of terrestrial water budget components over High Mountain Asia.

This study explores the uncertainties in terrestrial water budget estimation over High Mountain Asia (HMA) using a suite of uncoupled land surface model (LSM) simulations. The uncertainty in the water balance components of precipitation (P), evapotranspiration (ET), runoff(R), and terrestrial water storage (TWS) is significantly impacted by the uncertainty in the driving meteorology, with precipitation being the most important boundary condition. Ten gridded precipitation datasets along with a mix of model-, satellite-, and gauge-based products, are evaluated first to assess their suitability for LSM simulations over HMA. The datasets are evaluated by quantifying the systematic and random errors of these products as well as the temporal consistency of their trends. Though the broader spatial patterns of precipitation are generally well captured by the datasets, they differ significantly in their means and trends. In general, precipitation datasets that incorporate information from gauges are found to have higher accuracy with low Root Mean Square Errors and high correlation coefficient values. An ensemble of LSM simulations with selected subset of precipitation products is then used to produce the mean annual fluxes and their uncertainty over HMA in P, ET, and R to be 2.11±0.45, 1.26±0.11, and 0.85±0.36 mm per day, respectively. The mean annual estimates of the surface mass (water) balance components from this model ensemble are comparable to global estimates from prior studies. However, the uncertainty/spread of P, ET, and R is significantly larger than the corresponding estimates from global studies. A comparison of ET, snow cover fraction, and changes in TWS estimates against remote sensing-based references confirms the significant role of the input meteorology in influencing the water budget characterization over HMA and points to the need for improving meteorological inputs.

Optimal Endoscopic Screening Interval for Early Detection of Gastric Cancer: a Single-Center Study.

BACKGROUND: The optimal endoscopic screening interval for early gastric cancer (EGC) detection still remains controversial. Thus, we performed this prospective study to clarify the optimal interval between endoscopic examinations for EGC detection. METHODS: A questionnaire survey for penultimate endoscopy and gastric cancer (GC) diagnosis interval was used; the findings were then analyzed. The patients were divided into two groups according to GC type and endoscopic examinations intervals. RESULTS: A total of 843 patients were enrolled. The endoscopic GC detection interval (P < 0.001), tumor location (P < 0.001), tumor size (P < 0.001), histology (P < 0.001), tumor stage (P < 0.001), and treatment modality (P < 0.001) showed significant differences in the univariate analysis between EGC and advanced gastric cancer (AGC). Endoscopic examination intervals below 2 years and 3 years were associated with higher proportions of EGC detection (adjusted odds ratio, 2.458 and 3.022, respectively) (P < 0.001). The patients with endoscopic examination to GC diagnosis interval of < 2 years showed significant differences in tumor size (P < 0.001), tumor stage (P < 0.001), and treatment modality (P < 0.001) compared to those with intervals of > 2 years and without screening. Similar results were observed in those with < 3-year intervals. CONCLUSION: Triennial endoscopic screening might be as effective as biennial screening in increasing the detection rate of EGC and the risk of subsequent curable endoscopic resections.

Experimental infection of cows with newly isolated Akabane virus strain (AKAV-7) causing encephalomyelitis.

Akabane virus (AKAV), an arthropod-transmitted bunyavirus, is a major cause of congenital abnormalities and encephalomyelitis in ruminants. In 2010, there was a major outbreak of encephalomyelitis in Korea and fifteen AKAV strains, including AKAV-7, were isolated from cows. To identify the neuropathogenicity of AKAV-7, we performed experimental infection of cows. Six-month-old female Korean Holstein dairy cattle were inoculated with AKAV-7 by various routes, including intracerebral (IC), intrasubarachnoid space (IS), subcutaneous (SC) and intravenous (IV); a separate group was vaccinated before intravenous infection. Five of the six cows in the IC group and two of the six cows in the IS group showed clinical signs such as locomotor ataxia and paralysis of the hind limbs. Three of six cows died after IC infection 9-12 days post infection (dpi). Histopathologic changes such as nonsuppurative encephalomyelitis were confirmed in various parts of the central nervous system in the IC, IS and SC groups. Early onset of neutralizing antibodies in the serum and lower viral mRNA levels in the peripheral blood mononuclear cells (PBMCs) and various tissues in the vaccinated group was noticeable compared to the unvaccinated group (IV group). We suggest that the AKAV vaccine currently used in Korea may be partially effective for protection against AKAV-7 in cows.

Optimization of spot-size converter for low polarization dependent loss of waveguide photodetector.

We present an optimization of spot-size converter (SSC) of waveguide photodetector (PD) for small polarization dependent loss (PDL). Beam-propagation method simulation gives responsivity for each polarization and SSC structure. From the calculated responsivity data, optimum structure of SSC is determined that can be implemented with a sufficient process tolerance. We confirm the optimization by measuring PDL of waveguide PD designed according to the structure obtained through the simulation.

Channel estimation and synchronization for polarization-division multiplexed CO-OFDM using subcarrier/polarization interleaved training symbols.

We propose and demonstrate the use of subcarrier/polarization-interleaved training symbols for channel estimation and synchronization in polarization-division multiplexed (PDM) coherent optical orthogonal frequency-division multiplexed (CO-OFDM) transmission. The principle, the computational efficiency, and the frequency-offset tolerance of the proposed method are described. We show that the use of subcarrier/polarization interleaving doubles the tolerance to the frequency offset between the transmit laser and the receiver's optical local oscillator as compared to conventional schemes. Using this method, we demonstrate 43-Gb/s PDM CO-OFDM transmission with 16-QAM subcarrier modulation over 5,200-km of ultra-large-area fiber.

Nonuniform output characteristics of laser diode with wet-etched spot-size converter.

We study the output characteristics of spot-size converter (SSC) integrated buried heterostructure (BH) laser diode (LD) by forming SSC with wet etching process. SSC-LD shows large chip-to-chip variation in threshold current(Ith) and slope efficiency (eta(slope)) compared to LD without SSC. Ith and eta(slope) are closely related with each other so that the front facet eta(slope) increases while the rear facet eta(slope) decreases with Ith. Far-field angle is also found to be proportional to the front facet eta(slope). The trends observed are explained clearly by a unidirectional loss occurring when photons travel from the front to rear facet.