Reversibly Adapting Configuration in Atomic Catalysts Enables Efficient Oxygen Electroreduction.

Single-atom catalysts (SACs) featuring M-N-C moieties have garnered significant attention as efficient electrocatalysts for the oxygen reduction reaction (ORR). However, the role of the dynamic M-N configuration of SACs induced by the derived frameworks under applied ORR potentials remains poorly understood. Herein, we conduct a comprehensive investigation using multiple operando techniques to assess the dynamic configurations of Cu SACs under various microstructural interface (MSI) regulations by anchoring atomic Cu on g-C3N4 and zeolitic imidazolate framework (ZIF) substrates. Cu SACs supported on g-C3N4 exhibit symmetric Cu-N configurations characterized by a reversibly adaptive nature under operational conditions, which leads to their excellent ORR catalytic activity. In contrast, the Cu-N configuration in ZIF-derived Cu SACs undergoes irreversible structural changes during the ORR process, in which the elongated Cu-N pair is unstable and breaks during the ORR, acting as a competing reaction against the ORR and resulting in high overpotential requirements. Crucially, operando time-resolved X-ray absorption spectroscopy (TR-XAS) and Raman results unequivocally reveal the reversibly adapting properties of the local Cu-N configuration in atomic Cu-anchored g-C3N4, which have been overlooked in numerous literatures. All findings provide valuable insights into the potential-driven characteristics of atomic electrocatalysts during target reactions and offer a systematic approach to study atomic electrocatalysts and their corresponding catalytic behaviors.

Design of low-threshold photonic-crystal surface-emitting lasers with confined gain regions by using selective area intermixing.

Photonic-crystal surface-emitting lasers have many promising properties over traditional semiconductor lasers and are regarded as the next-generation laser sources. However, the minimum achievable lasing threshold of PCSELs is still several times larger than that of VCSELs, and limiting its applications especially if the required power is small. Here, we propose a new design that reduces the gain region in the lateral plane by using selective quantum-well intermixing to reduce the threshold current of PCSELs. By performing theoretical calculations, we confirmed that the threshold current can be lowered by a factor of two to three while keeping the PCSEL's advantage of small divergence angle.

Long-term outcomes of mitral valve replacement in dialysis patients: evidence from a nationwide database.

BACKGROUND: To compare the late outcomes between mechanical and bioprostheses after isolated mitral valve replacement (MVR) in dialysis-dependent patients. METHODS: A nationwide propensity-matched retrospective cohort study was conducted involving dialysis patients who underwent primary mitral replacement between 2001 and 2018. Ten-year postoperative outcomes were compared between mitral bioprosthesis and mechanical prosthesis using the Cox proportional hazard model and restricted mean survival time (RMST). RESULTS: The all-cause mortality was 20.8 and 13.0 events per 100 person-years, with a 10-year RMST of 7.40 and 7.31 years for bioprosthesis and mechanical prosthesis, respectively. Major bleeding was the most common adverse event for both bioprosthesis and mechanical prosthesis, with an incidence rate of 19.5 and 19.1 events per 100 person-years, respectively. The incidence of valve reoperation was higher among those who received bioprosthesis (0.55 events per 100 person-years). After 1:1 matching, the all-cause mortality was 15.45 and 14.54 events per 100 person-years for bioprosthesis and mechanical prosthesis, respectively. The RMST at 10 years was comparable between the two groups after matching (5.10 years for bioprosthesis vs. 4.59 years for mechanical prosthesis), with an RMST difference of -0.03. Further, no difference was observed in the incidence of major adverse valve-related events between bioprosthesis and mechanical valves. However, bioprosthesis was associated with a higher incidence of mitral valve reoperation among all major adverse events (RMST difference -0.24 years, 95% CI -0.48 to -0.01, P =0.047). CONCLUSIONS: This study found no association between valve selection and long-term survival outcomes in dialysis patients after MVR. However, bioprosthetic valves may be associated with a slightly higher incidence of reoperation, while other valve-related adverse events, including major bleeding and stroke, were comparable between the two types of prostheses.

Lewis Acidic Support Boosts C-C Coupling in the Pulsed Electrochemical CO2 Reaction.

Copper-oxide electrocatalysts have been demonstrated to effectively perform the electrochemical CO2 reduction reaction (CO2RR) toward C2+ products, yet preserving the reactive high-valent CuOx has remained elusive. Herein, we demonstrate a model system of Lewis acidic supported Cu electrocatalyst with a pulsed electroreduction method to achieve enhanced performance for C2+ products, in which an optimized electrocatalyst could reach ∼76% Faradaic efficiency for C2+ products (FEC2+) at ∼-0.99 V versus reversible hydrogen electrode, and the corresponding mass activity can be enhanced by ∼2 times as compared to that of conventional CuOx. In situ time-resolved X-ray absorption spectroscopy investigating the dynamic chemical/physical nature of Cu during CO2RR discloses that an activation process induced by the KOH electrolyte during pulsed electroreduction greatly enriched the Cuδ+O/Znδ+O interfaces, which further reveals that the presence of Znδ+O species under the cathodic potential could effectively serve as a Lewis acidic support for preserving the Cuδ+O species to facilitate the formation of C2+ products, and the catalyst structure-property relationship of Cuδ+O/Znδ+O interfaces can be evidently realized. More importantly, we find a universality of stabilizing Cuδ+O species for various metal oxide supports and to provide a general concept of appropriate electrocatalyst-Lewis acidic support interaction for promoting C2+ products.

Separated electrodes for the enhancement of high-speed data transmission in vertical-cavity surface-emitting laser arrays.

In this work, a novel design for the electrodes in a near quasi-single-mode (QSM) vertical-cavity surface-emitting laser (VCSEL) array with Zn-diffusion apertures inside is demonstrated to produce an effective improvement in the high-speed data transmission performance. By separating the electrodes in a compact 2×2 coupled VCSEL array into two parts, one for pure dc current injection and the other for large ac signal modulation, a significant enhancement in the high-speed data transmission performance can be observed. Compared with the single electrode reference, which parallels 4 VCSEL units in the array, the demonstrated array with its separated electrode design exhibits greater dampening of electrical-optical (E-O) frequency response and a larger 3-dB E-O bandwidth (19 vs. 15 GHz) under the same amount of total bias current (20 mA). Moreover, this significant improvement in dynamic performance does not come at the cost of any degradation in the static performance in terms of the maximum near QSM optical output power (17 mW @ 20 mA) and the Gaussian-like optical far-field pattern which has a narrow divergence angle (full-width half maximum (FWHM): 10° at 20 mA). The advantages of the separated electrode design lead to a much better quality of 32 Gbit/sec eye-opening as compared to that of the reference device (jitter: 1.5 vs. 2.8 ps) and error-free 32 Gbit/sec transmissions over a 500 m multi-mode fiber has been achieved under a moderate total bias current of 20 mA.

Pseudophakic pupillary block after phacoemulsification and posterior chamber intraocular lens implantation: Cause identification and treatment refinement.

BACKGROUND: Pseudophakic pupillary block (PPB) was rare in patients who undergo phacoemulsification and posterior chamber intraocular lens (PCIOL) implantation. Laser peripheral iridotomy was the most reported but ineffective treatment in the literature. METHODS: Retrospective, interventional case series of patients who developed PPB in Taipei Veterans General Hospital from 2017 to 2021. Clinical course, diagnostic methods, treatment and outcomes were recorded and discussed. RESULTS: Four eyes of three patients were documented. All of them had diabetes and diabetic retinopathy. Anterior segment Optical coherence tomography (OCT) of these patients showed an exudative membrane at the peripapillary area while slit lamp image could not provide a clear view due to the severely edematous corneal condition. Laser peripheral iridotomy and yttrium aluminum garnet (YAG) laser aiming to the peripapillary exudation were applied to break the PPB successfully. CONCLUSION: Diabetes mellitus, intravitreal injection and inflammation are crucial risk factors for PPB. Anterior segment OCT can be a useful diagnostic tool for the detection of the peripapillary exudative membrane while corneal clarity is compromised due to high intraocular pressure. In addition to peripheral laser iridotomy, an effective approach to resolve PPB may be the use of the YAG laser to break the exudative membrane.

MOF-Templated Sulfurization of Atomically Dispersed Manganese Catalysts Facilitating Electroreduction of CO2 to CO.

To reach a carbon-neutral future, electrochemical CO2 reduction reaction (eCO2RR) has proven to be a strong candidate for the next-generation energy system. Among potential materials, single-atom catalysts (SACs) serve as a model to study the mechanism behind the reduction of CO2 to CO, given their well-defined active metal centers and structural simplicity. Moreover, using metal-organic frameworks (MOFs) as supports to anchor and stabilize central metal atoms, the common concern, metal aggregation, for SACs can be addressed well. Furthermore, with their turnability and designability, MOF-derived SACs can also extend the scope of research on SACs for the eCO2RR. Herein, we synthesize sulfurized MOF-derived Mn SACs to study effects of the S dopant on the eCO2RR. Using complementary characterization techniques, the metal moiety of the sulfurized MOF-derived Mn SACs (MnSA/SNC) is identified as MnN3S1. Compared with its non-sulfur-modified counterpart (MnSA/NC), the MnSA/SNC provides uniformly superior activity to produce CO. Specifically, a nearly 30% enhancement of Faradaic efficiency (F.E.) in CO production is observed, and the highest F.E. of approximately 70% is identified at -0.45 V. Through operando spectroscopic characterization, the probing results reveal that the overall enhancement of CO production on the MnSA/SNC is possibly caused by the S atom in the local MnN3S1 moiety, as the sulfur atom may induce the formation of S-O bonding to stabilize the critical intermediate, *COOH, for CO2-to-CO. Our results provide novel design insights into the field of SACs for the eCO2RR.

Flow signal change in polyps after anti-vascular endothelial growth factor therapy.

Optical coherence tomography angiography (OCTA) is a novel, non-invasive imaging tool used to detect vascular flow. The absence of a flow signal in OCTA in polyps revealed by indocyanine green angiography (ICGA) in patients with polypoidal choroidal vasculopathy (PCV) may indicate slow or compromised filling of blood flow from choroidal vessels. Naïve patients with PCV treated with intravitreal injections of aflibercept (IVI-A) were enrolled in this study to validate the hypothesis that baseline flow may affect the outcome of polyp regression in ICGA. The flow signal of polyps in OCTA was detected by manual segmentation in the corresponding location by ICGA. Polyps were defined as high-flow if both OCTA and ICGA showed positive findings, and low-flow if OCTA showed a negative flow signal in 3 consecutive horizontal scans at the polyp area shown in ICGA. A total of 24 polyps were identified in 13 PCV patients at baseline. Of these 24 polyps, 22 (91.7%) were high-flow and 2 (8.3%) were low-flow. After 3 monthly IVI-A, all low-flow polyps had complete regression in ICGA. Among 17 (77%) high-flow polyps at baseline that had regression after treatment, 10 (58.8%) became low-flow, while 5 (22.7%) persistent polyps remained high-flow. Flow signal of polyps as detected by OCTA could be a predictive factor for treatment response in patients with PCV. Monitoring changes in flow signal after treatment is clinically relevant.

Dynamic Reoxidation/Reduction-Driven Atomic Interdiffusion for Highly Selective CO2 Reduction toward Methane.

Understanding the dynamic structural reconstruction/transformation of catalysts during electrochemical CO2 reduction reaction (CO2RR) is highly desired for developing more efficient and selective catalysts, yet still lacks in-depth realization. Herein, we study a model system of copper nanowires with various degrees of silver modifications as electrocatalysts for CO2RR. Among them, the Cu68Ag32 nanowire catalyst achieves the highest activity and selectivity toward methane with an extremely high faradaic efficiency of ∼60%, about 3 times higher than that of primitive Cu nanowires, and even surpasses the most efficient catalysts for producing methane. By using in situ grazing-angle X-ray scattering/diffraction, X-ray absorption spectroscopy, and Raman techniques, we found that the Cu68Ag32 nanowires underwent an irreversible structural reconstruction and well-stabilized chemical state of Cu on the catalyst surface under the working CO2RR conditions, which greatly facilitates the CO2 to methane conversion. Further analysis reveals that the restructuring phenomenon can be ascribed to a reoxidation/reduction-driven atomic interdiffusion between Cu and Ag. This work reveals the first empirical demonstration by deploying comprehensive in situ techniques to track the dynamic structural reconstruction/transformation in a model bimetallic system, which not only establishes a good understanding of the correlation between catalyst surface structure and catalytic selectivity but also provides deep insights into designing more developed electrocatalysts for CO2RR and beyond.

Reproducible and Bendable SERS Substrates with Tailored Wettability Using Block Copolymers and Anodic Aluminum Oxide Templates.

Surface properties are essential for substrates exhibiting high sensitivity in surface-enhanced Raman scattering (SERS) applications. In this work, novel SERS hybrid substrates using polystyrene-block-poly(methyl methacrylate) and anodic aluminum oxide templates is presented. The hybrid substrates not only possess hierarchical porous nanostructures but also exhibit superhydrophilic surface properties with the water contact angle ≈0°. Such surfaces play an important role in providing uniform enhanced intensities over large areas (relative standard deviation ≈10%); moreover, these substrates are found to be highly sensitive (limit of detection ≈10-12 m for rhodamine 6G (R6G)). The results show that the hybrid SERS substrates can achieve the simultaneous detection of multicomponent mixtures of different target molecules, such as R6G, crystal violet, and methylene blue. Furthermore, the bending experiments show that about 70% of the SERS intensities are maintained after bending from ≈30° to 150°.

Defect Passivation by Amide-Based Hole-Transporting Interfacial Layer Enhanced Perovskite Grain Growth for Efficient p-i-n Perovskite Solar Cells.

In this study, we synthesized four acceptor-donor-acceptor type hole-transporting materials (HTMs) of SY1-SY4 for an HTMs/interfacial layer with carbazole as the core moiety and ester/amide as the acceptor unit. These HTMs contain 4-hexyloxyphenyl substituents on the carbazole N atom, with extended π-conjugation achieved through phenylene and thiophene units at the 3,6-positions of the carbazole. When using amide-based HTMs SY2 as a dopant-free HTM in a p-i-n perovskite solar cell (PSC), we achieved a power conversion efficiency (PCE) of 13.59% under AM 1.5G conditions (100 mW cm-2); this PCE was comparable with that obtained when using PEDOT:PSS as the HTM (12.33%). Amide-based SY2 and SY4 HTMs showed a larger perovskite grain than SY1 and SY3 because of the passivation of traps/defects at the grain boundaries and stronger interaction with the perovskite layer. In further investigation, we demonstrated highly efficient and stable PSCs when using the dopant-free p-i-n device structure indium tin oxide/NiOx/interfacial layer (SY-HTMs)/perovskite/PC61BM/BCP/Ag. The interfacial layer improved the PCEs and large grain size (micrometer scale) of the perovskite layer because of defect passivation and interface modification; the amide group exhibited a Lewis base adduct property coordinated to Ni and Pb ions in NiOx and perovskite, bifacial defect passivation and reduced the grain boundaries to improve the crystallinity of the perovskite. The amide-based SY2 exhibited the stronger interaction with the perovskite layer than that of ester-based SY1, which is related to the observations in X-ray absorption near edge structure (XANES). The best performance of the NiOx/SY2 device was characterized by a short-circuit current density (Jsc) of 21.76 mA cm-2, an open-circuit voltage (Voc) of 1.102 V, and a fill factor of 79.1%, corresponding to an overall PCE of 18.96%. The stability test of the PCE of the NiOx/SY2 PSC device PCE showed a decay of only 5.01% after 168 h; it retained 92.01% of its original PCE after 1000 h in Ar atmosphere. Time-resolved photoluminescence spectra of the perovskite films suggested that the hole extraction capabilities of the NiOx/SY-HTMs were better than that of the bare NiOx. The superior film morphologies of the NiOx/SY-HTMs were responsible for the performances of their devices being comparable with those of bare NiOx-based PSCs. The photophysical properties of the HTMs were analyzed through time-dependent density functional theory with the B3LYP functional.

Revealing the structural transformation of rutile RuO2via in situ X-ray absorption spectroscopy during the oxygen evolution reaction.

RuO2 has been generally considered as the most active catalyst for the oxygen evolution reaction (OER) to date and shows remarkably higher activity in an acidic electrolyte than under alkaline conditions. Nevertheless, the dynamic valence state and local structure of reactive centers (i.e., Ru) in both acidic and alkaline electrolytes have not been systematically investigated yet, especially through in situ approaches. Herein, we employed in situ X-ray absorption spectroscopy to study the dynamic valence state and local structure of RuO2 during the OER in both acidic and alkaline electrolytes. In the acidic electrolyte, the Ru center was reduced near the onset potential prior to launching the OER and was oxidized during the OER process, while the coordination numbers and the bond lengths of the Ru-O path also decreased as revealed by in situ EXAFS analysis. Besides, in the alkaline electrolyte, RuO2 showed a similar behavior as revealed under acidic conditions. These results provide an evident insight into the dynamic change of the RuO2 electrocatalyst during the OER.

Quantitatively Unraveling the Redox Shuttle of Spontaneous Oxidation/Electroreduction of CuO x on Silver Nanowires Using in Situ X-ray Absorption Spectroscopy.

Oxide-derived copper catalysts have been shown to enhance CO2 reduction reaction (CO2RR) activity with high selectivity toward hydrocarbon products. However, the chemical state of oxide-derived copper during the CO2RR has remained elusive and is lacking in situ observations. Herein, a two-step process was developed to synthesize Ag nanowires coated with various thicknesses of a CuO x layer for the CO2RR. By employing in situ X-ray absorption spectroscopy, a strong correlation between the chemical state under reaction conditions and the CO2RR product profile can be revealed to validate another competing reaction (i.e., the spontaneous oxidation of Cu(0) in aqueous electrolyte) that significantly governs the chemical state of active centers of Cu. In situ Raman spectroscopy reveals the existence of reoxidation behavior under cathodic potential, and the quantification analysis of reoxidized behavior is revealed to indicate that the reoxidation rate is independent of surface morphology and strongly proportional to the electrochemically surface area. The steady oxidation state of Cu in an in situ condition is the paramount key and dominates the products' profile of the CO2RR rather than other factors (e.g., crystal facets, atomic arrangements, morphology, elements) that have been investigated in numerous reports.

Bilateral anterior uveitis after immunotherapy for malignant melanoma.

Immune checkpoint blockade therapy is relatively a new treatment for cancer which has shown promising results. However, immune-related side effects including uveitis have occasionally been reported during this therapy. Herein, we report the case of a 65-year-old male who suffered bilateral anterior uveitis after immune checkpoint blockade therapy with pembrolizumab and ipilimumab for malignant melanoma. His symptoms and signs improved after topical treatment with corticosteroids. Clinicians should be aware that uveitis can be an immune-related adverse event of immunotherapy.

Effects of Nanoscale V-Shaped Pits on GaN-Based Light Emitting Diodes.

This paper reviews the formation of nanoscale V-shaped pits on GaN-based light emitting diodes (LEDs) grown by the metal organic chemical vapor deposition (MOCVD) system and studies the effect of V-shaped pits on quantum efficiency. Since V-pits could provide potential barriers around threading dislocations to lessen non-radiative recombinations in such a high defect environment. In our study, multiple InGaN/GaN quantum well samples with different emission wavelengths of 380, 420, 460, and 500 nm were grown, each with different nanoscale V-shaped pits of three diameters for 150, 200, and 250 nm, respectively. It was found that the multiple quantum well (MQW) sample with larger V-pits had a lower pit density, but a relatively larger total V-pits defected area. The optimum diameter of V-pits showing the highest quantum efficiency from the MQW sample depended on the emission wavelength. MQW samples with wavelengths of 380 and 500 nm exhibited the best internal quantum efficiency (IQE) performance at the smallest V-pits area; however, the best performance for MQW samples with wavelength around 420 and 460 nm occurred when large V-pit areas were presented. Photoluminescence (PL) peak shifts and Raman shifts can provide a relationship between quantum-confined Stark effect (QCSE) and IQE, as well as a comparison between strain and IQE. The results obtained in this phenomenological study shall provide a useful guide line in making high-performance GaN-based LEDs with wide emission spectra.

Encouraging overweight students with intellectual disability to actively perform walking activity using an air mouse combined with preferred stimulation.

This study continues the research on using an air mouse as a physical activity detector. An air mouse is embedded with a MEMS (Micro Electro Mechanical Systems) gyro sensor, which can measure even the slightest movement in the air. The air mouse was strapped to one of each participant's calves to detect walking activity. This study was conducted to evaluate whether four students with intellectual disability who were overweight and disliked exercising could be motivated to engage in walking actively by linking the target response with preferred stimulation. Single-subject research with ABAB design was adopted in this study. The experimental data showed substantial increases in the participants' target responses (i.e. the performance of the activity of walking) during the intervention phases compared to the baseline phases. The practical and developmental implications of the findings are discussed.