Exploring Doping Mechanisms and Modulating Carrier Concentration in Copper Iodide: Applications in Thermoelectric Materials.

Due to its small hole-effective mass, flexibility, and transparency, copper iodide (CuI) has emerged as a promising p-type alternative to the predominantly used n-type metal oxide semiconductors. However, the lack of effective doping methods hinders the utility of CuI in various applications. Sulfur (S)-doping through liquid iodination is previously reported to significantly enhance electrical conductivity up to 511 S cm-1. In this paper, the underlying doping mechanism with various S-dopants is explored, and suggested a method for controlling electrical conductivity, which is important to various applications, especially thermoelectric (TE) materials. Subsequently, electric and TE properties are systematically controlled by adjusting the carrier concentration from 3.0 × 1019 to 4.5 × 1020 cm-3, and accurately measured thermal conductivity with respect to carrier concentration and film thickness. Sulfur-doped CuI (CuI:S) thin films exhibited a maximum power factor of 5.76 µW cm-1 K-2 at a carrier concentration of 1.3 × 1020 cm-3, and a TE figure of merit (ZT) of 0.25. Furthermore, a transparent and flexible TE power generator is developed, with an impressive output power density of 43 nW cm-2 at a temperature differential of 30 K. Mechanical durability tests validated the potential of CuI:S films in transparent and flexible TE applications.

Predicting serious postoperative complications and evaluating racial fairness in machine learning algorithms for metabolic and bariatric surgery.

BACKGROUND: Predicting the risk of complications is critical in metabolic and bariatric surgery (MBS). OBJECTIVES: To develop machine learning (ML) models to predict serious postoperative complications of MBS and evaluate racial fairness of the models. SETTING: Metabolic and Bariatric Surgery Accreditation and Quality Improvement Program (MBSAQIP) national database, United States. METHODS: We developed logistic regression, random forest (RF), gradient-boosted tree (GBT), and XGBoost model using the MBSAQIP Participant Use Data File from 2016 to 2020. To address the class imbalance, we randomly undersampled the complication-negative class to match the complication-positive class. Model performance was evaluated using the area under the receiver operating characteristic curve (AUROC), precision, recall, and F1 score. Fairness across White and non-White patient groups was assessed using equal opportunity difference and disparate impact metrics. RESULTS: A total of 40,858 patients were included after undersampling the complication-negative class. The XGBoost model was the best-performing model in terms of AUROC; however, the difference was not statistically significant. While the F1 score and precision did not vary significantly across models, the RF exhibited better recall compared to the logistic regression. Surgery type was the most important feature to predict complications, followed by operative time. The logistic regression model had the best fairness metrics for race. CONCLUSIONS: The XGBoost model achieved the highest AUROC, albeit without a statistically significant difference. The RF may be useful when recall is the primary concern. Undersampling of the privileged group may improve the fairness of boosted tree models.

Junctionless Structure Indium-Tin Oxide Thin-Film Transistors Enabling Enhanced Mechanical and Contact Stability.

In recent years, considerable attention has focused on high-performance and flexible crystalline metal oxide thin-film transistors (TFTs). However, achieving both high performance and flexibility in semiconductor devices is challenging due to the inherently conductive and brittle nature of crystalline metal oxide. In this study, we propose a facile way to overcome this limitation by employing a junctionless (JL) TFT structure via oxygen plasma treatment of the crystalline indium-tin oxide (ITO) films. The oxygen plasma treatment significantly reduced oxygen vacancies in the ITO films, contributing to the significant reduction in the carrier concentration from 4.67 × 1020 to 1.39 × 1016. Importantly, this reduction was achieved without inducing any noticeable structural changes in the ITO, enabling the successful realization of ITO JL TFTs with an adjustable threshold voltage. Furthermore, the ITO JL TFTs demonstrate good stability and reliability under various bias stress conditions, aging in the air atmosphere, and high-temperature processes. In addition, the ITO JL TFTs exhibit low light sensitivity due to the wide bandgap of ITO and further suppression of Vo defects, making them suitable for applications requiring stable performance under light exposure. To compare and analyze the flexibility of the JL structure and conventional structure with additional source/drain (S/D) junction in ITO TFTs with nonencapsulation, we utilized mechanical simulations and transmission line method (TLM). By employing the JL structure in ITO TFT through carefully optimized oxygen plasma treatment, we successfully mitigated stress concentration at the S/D-channel interface. This resulted in a JL ITO TFT that exhibited a change in contact resistance of less than 20% even after 20,000 bending cycles. Consequently, a stable and flexible ITO TFT with field-effect mobility (µFE) of 12.74 cm2/(V s) was realized, outperforming conventionally structured ITO TFTs with additional S/D junction, where the contact resistance nearly tripled.

Tailored Postsynthetic Nitration of a Hypercrosslinked Polymer for Single-Step Ethylene Purification from a Ternary C2 Gas Mixture.

Purifying C2H4 from a ternary C2H2/C2H4/C2H6 mixture poses a substantial industrial challenge due to their close physical and chemical properties. In this study, we introduce an innovative design approach to regulate and optimize the nitration degree of a hypercrosslinked polymer to achieve targeted separation performance. We synthesized a porous organic polymer (HCP) using the solvent knitting method and carried out its postsynthetic nitration, resulting in HCP-NO2-1 and HCP-NO2-2 with different nitration degrees. Notably, the adsorption capacity shifted from C2H6 > C2H4 ≈ C2H2 for HCP to C2H2 > C2H6 > C2H4 for HCP-NO2-1 and to C2H2 > C2H4 ≈ C2H6 for HCP-NO2-2, demonstrating the controllable nature of the separation process via the polar nitro group insertion. Remarkably, HCP-NO2-1 exhibited a desirable, selective separation of C2H4 from the C2H6/C2H4/C2H2 mixture thanks to an exquisite combination of the acidic proton-polar nitro group and nonpolar C-H∙∙∙π interactions. Separation capability was further corroborated by computational simulations and breakthrough tests. This work marks a significant advancement as the first successful postsynthetic functionalization strategy for C2H4 purification from a ternary gas mixture among porous organic polymers.

Simultaneous Protonation and Metalation of a Porphyrin Covalent Organic Framework Enhance Photodynamic Therapy.

Covalent organic frameworks (COFs) have been explored for photodynamic therapy (PDT) of cancer, but their antitumor efficacy is limited by excited state quenching and low reactive oxygen species generation efficiency. Herein, we report a simultaneous protonation and metalation strategy to significantly enhance the PDT efficacy of a nanoscale two-dimensional imine-linked porphyrin-COF. The neutral and unmetalated porphyrin-COF (Ptp) and the protonated and metalated porphyrin-COF (Ptp-Fe) were synthesized via imine condensation between 5,10,15,20-tetrakis(4-aminophenyl)porphyrin and terephthalaldehyde in the absence and presence of ferric chloride, respectively. The presence of ferric chloride generated both doubly protonated and Fe3+-coordinated porphyrin units, which red-shifted and increased the Q-band absorption and disrupted exciton migration to prevent excited state quenching, respectively. Under light irradiation, rapid energy transfer from protonated porphyrins to Fe3+-coordinated porphyrins in Ptp-Fe enabled 1O2 and hydroxyl radical generation via type II and type I PDT processes. Ptp-Fe also catalyzed the conversion of hydrogen peroxide to hydroxy radical through a photoenhanced Fenton-like reaction under slightly acidic conditions and light illumination. As a result, Ptp-Fe-mediated PDT exhibited much higher cytotoxicity than Ptp-mediated PDT on CT26 and 4T1 cancer cells. Ptp-Fe-mediated PDT afforded potent antitumor efficacy in subcutaneous CT26 murine colon cancer and orthotopic 4T1 murine triple-negative breast tumors and prevented metastasis of 4T1 breast cancer to the lungs. This work underscores the role of fine-tuning the molecular structures of COFs in significantly enhancing their PDT efficacy.

Cost-effectiveness analysis of the 20-valent pneumococcal conjugate vaccine for the pediatric population in South Korea.

OBJECTIVES: To evaluate the cost-effectiveness of the 20-valent pneumococcal conjugate vaccine (PCV20) compared to 13-valent pneumococcal conjugate vaccine (PCV13) for the pediatric population in Korea, where the four-dose vaccine coverage rate is over 97%. METHODS: We constructed a Markov model to calculate the cost and quality-adjusted life-years (QALYs) over 10 years. The health states were susceptible states; disease states, which included invasive pneumococcal diseases such as meningitis, bacteremia, pneumonia, and acute otitis media; and death attributable to pneumococcal disease. The annual incidence and mortality due to pneumococcal diseases were estimated based on the serotypes covered by PCV13 and PCV20, vaccine coverage rate, vaccine effectiveness, and population size. Vaccine, administration, and disease costs were included in the model. RESULTS: In the total population (n = 51,431,305), PCV20 prevented more pneumococcal diseases and deaths, resulting in a gain of 74,855 QALY over PCV13. Meanwhile, the PCV20 group spent $275,136,631 less than the PCV13 group. As PCV20 gained more QALYs but spent less on total medical costs than PCV13, PCV20 was dominant over PCV13. CONCLUSIONS: In the Korean population, PCV20 is a cost-effective and dominant option over PCV13. Our findings provide evidence for decision-making regarding the introduction of PCV20 in countries with high vaccine coverage.

Photoexcited Carrier Dynamics in Iodine-Doped CH3NH3PbBr3 Single Crystals.

Iodine-doped bromide perovskite single crystals (IBPSCs) have important applications in optoelectronic fields, such as in solar cells. Currently, much research has aimed to study the phase separation phenomenon and device performance improvements in IBPSCs. However, important intrinsic photoexcited carrier dynamics are often overlooked in IBPSCs. Here, we explored the photoexcited carrier dynamics in typical iodine-doped MAPbBr3 single crystals using the excitation intensity-dependent steady-state photoluminescence (PL) and time-resolved photoluminescence (TRPL) technique. We found that the trap state density changes with an increase in the amount of doped iodine. Further, we noticed that there is an influence of carrier diffusion on the photoexcited carrier dynamics, and then, we evaluated the carrier diffusion coefficients and recombination constants via numerical simulations of the PL kinetics. Consequently, we found that the electron shallow trap-related carrier behaviors substantially impacted the PL kinetics. Our results greatly facilitate a deeper understanding of the fundamental characteristics of mixed halide perovskite material.

Disturbed flow regulates protein disulfide isomerase A1 expression via microRNA-204.

Redox processes can modulate vascular pathophysiology. The endoplasmic reticulum redox chaperone protein disulfide isomerase A1 (PDIA1) is overexpressed during vascular proliferative diseases, regulating thrombus formation, endoplasmic reticulum stress adaptation, and structural remodeling. However, both protective and deleterious vascular effects have been reported for PDIA1, depending on the cell type and underlying vascular condition. Further understanding of this question is hampered by the poorly studied mechanisms underlying PDIA1 expression regulation. Here, we showed that PDIA1 mRNA and protein levels were upregulated (average 5-fold) in the intima and media/adventitia following partial carotid ligation (PCL). Our search identified that miR-204-5p and miR-211-5p (miR-204/211), two broadly conserved miRNAs, share PDIA1 as a potential target. MiR-204/211 was downregulated in vascular layers following PCL. In isolated endothelial cells, gain-of-function experiments of miR-204 with miR mimic decreased PDIA1 mRNA while having negligible effects on markers of endothelial activation/stress response. Similar effects were observed in vascular smooth muscle cells (VSMCs). Furthermore, PDIA1 downregulation by miR-204 decreased levels of the VSMC contractile differentiation markers. In addition, PDIA1 overexpression prevented VSMC dedifferentiation by miR-204. Collectively, we report a new mechanism for PDIA1 regulation through miR-204 and identify its relevance in a model of vascular disease playing a role in VSMC differentiation. This mechanism may be regulated in distinct stages of atherosclerosis and provide a potential therapeutic target.

A nationwide analysis of the treatment patterns, survival, and medical costs in Korean patients with relapsed or refractory diffuse large B-cell lymphoma.

Background: Approximately one-third of patients with diffuse large B-cell lymphoma (DLBCL) are refractory to treatment or experience relapse after initial therapy. Unfortunately, treatment options for older patients and those who experience relapse or become refractory to hematopoietic stem cell transplantation (HSCT) are limited. This nationwide population-based study aimed to identify treatment patterns, survival times, and treatment costs in patients with relapsed/refractory DLBCL (R/R DLBCL). Materials and methods: Between 2011 and 2020, data on patients with R/R DLBCL were retrieved from the Korean Health Insurance Review & Assessment Service, encompassing the entire population. We identified the treatment patterns for each treatment line using a Sankey diagram and calculated the median time to the subsequent treatment in line. Median overall and progression-free survival times were estimated using the Kaplan-Meier survival curves. Finally, the medical costs incurred during DLBCL treatment were calculated for each treatment line and the costs related to HSCT were summarized at the episode level. Results: A total of 864 patients with R/R DLBCL who received second-line treatment were identified, and a regimen of ifosfamide, carboplatin, and etoposide (ICE) was administered the most. Among them, 353 were refractory or relapsed cases that were treated with third-line treatments. The median times for second-line to third-line, third-line to fourth-line, fourth-line to fifth-line, and fifth-line to sixth-line treatment failures gradually decreased (3.93, 2.86, 1.81, and 1.38 months, respectively). The median overall survival time was 8.90 and 4.73 months following the second-line and third-line treatments, respectively. In the third-line treatment setting, the patients did not show a significant difference in survival time after HSCT. The median medical cost was $39,491 across all treatment lines including the cost of HSCT which was $22,054. Conclusion: The treatment patterns in patients with R/R DLBCL, especially at third-line treatments and thereafter, were complicated, and their prognosis was poor despite the high medical costs. Novel and effective treatment options are expected to improve the prognosis and alleviate the economic burden of patients with R/R DLBCL.

Comparative efficacy of vericiguat to sacubitril/valsartan for patients with heart failure reduced ejection fraction: Systematic review and network meta-analysis.

BACKGROUND: Despite the established efficacy of vericiguat compared to placebo, uncertainties remain regarding its comparative efficacy to sacubitril/valsartan for patients with heart failure reduced ejection fraction (HFrEF). This study aimed to assess the relative efficacy of vericiguat and sacubitril/valsartan through a systematic review, network meta-analysis, and non-inferiority tests. METHODS: A systematic review was conducted to identify the randomized phase 3 clinical trials involving vericiguat and sacubitril/valsartan. The hazard ratios (HRs) with 95% confidence intervals (CI) for cardiovascular death (CVD) and hospitalization due to HF (hHF) were extracted from these trials and synthesized via network meta-analysis. Non-inferiority testing of vericiguat was performed using a fixed-margin method with a predefined non-inferiority margin (1.24). Sensitivity analyses explored the impact of the time from hHF to screening. RESULTS: Among the 1366 studies, two trials (VICTORIA and PARADIGM-HF) met the inclusion criteria. Network meta-analysis demonstrated that the HR for CVD or hHF with vericiguat did not significantly differ from that for sacubitril/valsartan (HR: 0.88, 95% CI:0.62-1.23). The upper limit of the 95% CI was less than the predefined margin of 1.24, confirming vericiguat's non-inferiority to sacubitril/valsartan. Sensitivity analyses affirmed the robustness of the base-case results. CONCLUSION: Vericiguat exhibited a comparable risk of CVD or hHF when contrasted with sacubitril/valsartan. Importantly, in patients with HFrEF, vericiguat's efficacy was not statistically inferior to that of sacubitril/valsartan. These findings reinforce the potential of vericiguat as a viable treatment option for this patient population.

Predicting operative time for metabolic and bariatric surgery using machine learning models: a retrospective observational study.

BACKGROUND: Predicting operative time is essential for scheduling surgery and managing the operating room. This study aimed to develop machine learning (ML) models to predict the operative time for metabolic and bariatric surgery (MBS) and to compare each model. METHODS: The authors used the Metabolic and Bariatric Surgery Accreditation and Quality Improvement Program database between 2016 and 2020 to develop ML models, including linear regression, random forest, support vector machine, gradient-boosted tree, and XGBoost model. Patient characteristics and surgical features were included as variables in the model. The authors used the mean absolute error, root mean square error, and R 2 score to evaluate model performance. The authors identified the 10 most important variables in the best-performing model using the Shapley Additive exPlanations algorithm. RESULTS: In total, 668 723 patients were included in the study. The XGBoost model outperformed the other ML models, with the lowest root mean square error and highest R 2 score. Random forest performed better than linear regression. The relative performance of the ML algorithms remained consistent across the models, regardless of the surgery type. The surgery type and surgical approach were the most important features to predict the operative time; specifically, sleeve gastrectomy (vs. Roux-en-Y gastric bypass) and the laparoscopic approach (vs. robotic-assisted approach) were associated with a shorter operative time. CONCLUSIONS: The XGBoost model best predicted the operative time for MBS among the ML models examined. Our findings can be useful in managing the operating room scheduling and in developing software tools to predict the operative times of MBS in clinical settings.

Cost-effectiveness of the 20-valent pneumococcal conjugate vaccine versus the 23-valent pneumococcal polysaccharide vaccine for older adults in South Korea.

BACKGROUND: Despite the demonstrated immunogenicity and safety of the 20-valent pneumococcal conjugate vaccine (PCV20) in older adults, the cost-effectiveness of the PCV20 was not examined compared to the 23-valent pneumococcal polysaccharide vaccine (PPSV23) in South Korea. Therefore, this study aimed to evaluate the cost-effectiveness of PCV20 compared with PPSV23 in adults aged 65 years and older in South Korea. METHODS: We constructed a Markov model that included susceptible states, invasive pneumococcal disease (IPD), non-bacteremic pneumonia (NBP), and death. The population was categorized by disease risk status (low risk, moderate risk, and high risk) and age group (65-74/75-84/85-99 years) at model entry. The annual incidence and mortality of IPD and NBP associated with PCV20 and PPSV23 were estimated based on serotype coverage, vaccine coverage, and vaccine effectiveness. The disease costs and utilities were obtained from previous studies. The incremental cost-effectiveness ratio (ICER) was used to evaluate cost-effectiveness within the threshold of 16,824 USD per quality-adjusted life-year (QALY). RESULTS: Among the total population (n = 8,843,072), PCV20 prevented 1941 and 50,575 cases of IPDs and NBPs, respectively, and 898 and 8593 deaths due to IPDs and NBPs compared to PPSV23. The total medical cost per person was 12.11 USD higher in PCV20, with a gain of 0.0053 LYs and 0.0045 QALYs per person. The ICER for PCV20 and PPSV23 was 2270 USD/LY and 2677 USD/QALY. CONCLUSIONS: In South Korea, PCV20 is a cost-effective option compared with PPSV23 for adults aged 65 years and older. These cost-effectiveness results provide evidence for decision-making regarding the approval and National Immunization Program implementation of PCV20.

Cost Effectiveness of Zanubrutinib Versus Ibrutinib in Relapsed or Refractory Chronic Lymphocytic Leukemia.

BACKGROUND: While the efficacy and safety of zanubrutinib have been established in relapsed or refractory chronic lymphocytic leukemia, the evidence on cost effectiveness is still lacking. OBJECTIVE: We aimed to evaluate the cost effectiveness of zanubrutinib versus ibrutinib in relapsed or refractory chronic lymphocytic leukemia from the commercial payer perspective in the USA. METHODS: A partitioned survival model was developed based on survival curves from the phase III ALPINE trial. We reconstructed patient-level data for each curve and conducted a parametric estimation to incorporate long-term clinical outcomes and treatment costs into the model. Medical costs and utilities were obtained from public data and previous cost-effectiveness studies. A discount rate of 3.0% per annum was applied and costs were adjusted to 2023 US dollars. The incremental cost-effectiveness ratio was calculated by dividing the incremental costs of zanubrutinib over ibrutinib by the incremental life-years or quality-adjusted life-years. Deterministic and probabilistic sensitivity analyses were performed to examine the robustness of the results. RESULTS: Over a 10-year analysis period, the incremental cost-effectiveness ratio of zanubrutinib versus ibrutinib was $91,260 per life-year gained and $120,634 per quality-adjusted life-year gained, making it cost effective within a threshold of $150,000 per quality-adjusted life-year gained. The incremental cost-effectiveness ratio was most sensitive to drug acquisition costs and progression-free survival distributions, and the probability of zanubrutinib being cost effective was approximately 52.8%, with a 30.0% likelihood of dominance. CONCLUSIONS: Zanubrutinib is likely to be cost effective versus ibrutinib in relapsed or refractory chronic lymphocytic leukemia in the USA, but the high threshold should be noted. Our findings may provide a basis for pricing strategy and reimbursement decisions for zanubrutinib.

Nanoscale Covalent Organic Framework with Staggered Stacking of Phthalocyanines for Mitochondria-Targeted Photodynamic Therapy.

Phthalocyanine photosensitizers (PSs) have shown promise in fluorescence imaging and photodynamic therapy (PDT) of malignant tumors, but their practical application is limited by the aggregation-induced quenching (AIQ) and inherent photobleaching of PSs. Herein, we report the synthesis of a two-dimensional nanoscale covalent organic framework (nCOF) with staggered (AB) stacking of zinc-phthalocyanines (ZnPc), ZnPc-PI, for fluorescence imaging and mitochondria-targeted PDT. ZnPc-PI isolates and confines ZnPc PSs in the rigid nCOF to reduce AIQ, improve photostability, enhance cellular uptake, and increase the level of reactive oxygen species (ROS) generation via mitochondrial targeting. ZnPc-PI shows efficient tumor accumulation, which allowed precise tumor imaging and nanoparticle tracking. With high cellular uptake and tumor accumulation, intrinsic mitochondrial targeting, and enhanced ROS generation, ZnPc-PI exhibits potent PDT efficacy with >95% tumor growth inhibition on two murine colon cancer models without causing side effects.

HEG1 Protects Against Atherosclerosis by Regulating Stable Flow-Induced KLF2/4 Expression in Endothelial Cells.

BACKGROUND: Atherosclerosis preferentially occurs in arterial regions of disturbed blood flow, and stable flow (s-flow) protects against atherosclerosis by incompletely understood mechanisms. METHODS: Our single-cell RNA-sequencing data using the mouse partial carotid ligation model was reanalyzed, which identified Heart-of-glass 1 (HEG1) as an s-flow-induced gene. HEG1 expression was studied by immunostaining, quantitive polymerase chain reaction, hybridization chain reaction, and Western blot in mouse arteries, human aortic endothelial cells (HAECs), and human coronary arteries. A small interfering RNA-mediated knockdown of HEG1 was used to study its function and signaling mechanisms in HAECs under various flow conditions using a cone-and-plate shear device. We generated endothelial-targeted, tamoxifen-inducible HEG1 knockout (HEG1iECKO) mice. To determine the role of HEG1 in atherosclerosis, HEG1iECKO and littermate-control mice were injected with an adeno-associated virus-PCSK9 [proprotein convertase subtilisin/kexin type 9] and fed a Western diet to induce hypercholesterolemia either for 2 weeks with partial carotid ligation or 2 months without the surgery. RESULTS: S-flow induced HEG1 expression at the mRNA and protein levels in vivo and in vitro. S-flow stimulated HEG1 protein translocation to the downstream side of HAECs and release into the media, followed by increased messenger RNA and protein expression. HEG1 knockdown prevented s-flow-induced endothelial responses, including monocyte adhesion, permeability, and migration. Mechanistically, HEG1 knockdown prevented s-flow-induced KLF2/4 (Kruppel-like factor 2/4) expression by regulating its intracellular binding partner KRIT1 (Krev interaction trapped protein 1) and the MEKK3-MEK5-ERK5-MEF2 pathway in HAECs. Compared with littermate controls, HEG1iECKO mice exposed to hypercholesterolemia for 2 weeks and partial carotid ligation developed advanced atherosclerotic plaques, featuring increased necrotic core area, thin-capped fibroatheroma, inflammation, and intraplaque hemorrhage. In a conventional Western diet model for 2 months, HEG1iECKO mice also showed an exacerbated atherosclerosis development in the arterial tree in both sexes and the aortic sinus in males but not in females. Moreover, endothelial HEG1 expression was reduced in human coronary arteries with advanced atherosclerotic plaques. CONCLUSIONS: Our findings indicate that HEG1 is a novel mediator of atheroprotective endothelial responses to flow and a potential therapeutic target.

A Spirobifluorene-Based Covalent Organic Framework for Dual Photoredox and Nickel Catalysis.

Covalent organic frameworks (COFs) have emerged as tunable, crystalline, and porous functional organic materials, but their application in photocatalysis has been limited by rapid excited-state quenching. Herein, we report the first example of dual photoredox/nickel catalysis by an sp2 carbon-conjugated spirobifluorene-based COF. Constructed from spirobifluorene and nickel-bipyridine linkers, the NiSCN COF adopted a two-dimensional structure with staggered stacking. Under light irradiation, NiSCN catalyzed amination and etherification/esterification reactions of aryl halides through the photoredox mechanism, with a catalytic efficiency more than 23-fold higher than that of its homogeneous control. NiSCN was used in five consecutive reactions without a significant loss of catalytic activity.

Controlled Crystal Growth of All-Inorganic CsPbI2.2Br0.8 Thin Film via Additive Strategy for Air-Processed Efficient Outdoor/Indoor Perovskite Solar Cells.

The evolution of defects during perovskite film fabrication deteriorates the overall film quality and adversely affects the device efficiency of perovskite solar cells (PSCs). We endeavored to control the formation of defects by applying an additive engineering strategy using FABr, which retards the crystal growth formation of CsPbI2.2Br0.8 perovskite by developing an intermediate phase at the initial stage. Improved crystalline and pinhole-free perovskite film with an optimal concentration of FABr-0.8M% additive was realized through crystallographic and microscopic analysis. Suppressed non-radiative recombination was observed through photoluminescence with an improved lifetime of 125 ns for FABr-0.8M% compared to the control film (83 ns). The champion device efficiency of 17.95% was attained for the FABr-0.8M% PSC, while 15.94% efficiency was achieved in the control PSC under air atmospheric conditions. Furthermore, an impressively high indoor performance of 31.22% was achieved for the FABr-0.8M% PSC under 3200 K (1000 lux) LED as compared to the control (23.15%). With a realistic approach of air processing and controlling the crystallization kinetics in wide-bandgap halide PSCs, this investigation paves the way for implementing additive engineering strategies to reduce defects in halide perovskites, which can further benefit efficiency enhancements in outdoor and indoor applications.

Single-Cell RNA sequencing investigation of female-male differences under PAD conditions.

Peripheral arterial disease (PAD) is an age-related medical condition affecting mostly muscular arteries of the limb. It is the 3rd leading cause of atherosclerotic morbidity. The mechanical environment of endothelial cells (ECs) in PAD is characterized by disturbed blood flow (d-flow) and stiff extracellular matrices. In PAD, the stiffness of arteries is due to decreased elastin function and increased collagen content. These flow and stiffness parameters are largely missing from current models of PAD. It has been previously proven that ECs exposed to d-flow or stiff substrates lead to proatherogenic pathways, but the effect of both, d-flow and stiffness, on EC phenotype has not been fully investigated. In this study, we sought to explore the effect of sex on proatherogenic pathways that could result from exposing endothelial cells to a d-flow and stiff environment. We utilized the scRNA-seq tool to analyze the gene expression of ECs exposed to the different mechanical conditions both in vitro and in vivo. We found that male ECs exposed to different mechanical stimuli presented higher expression of genes related to fibrosis and d-flow in vitro. We validated our findings in vivo by exposing murine carotid arteries to d-flow via partial carotid artery ligation. Since women have delayed onset of arterial stiffening and subsequent PAD, this work may provide a framework for some of the pathways in which biological sex interacts with sex-based differences in PAD.

Long-term effects of chromium from red mud (bauxite residue) ocean dumping on the benthic environment in South Korea.

Between 1999 and 2009, 344,000 m3 of red mud was released into the red mud dumping zone in the East Sea-Byeong ocean dumping site in South Korea. This study aimed to assess the impacts before and after the 2010 red mud dumping ban. We quantified total Cr concentrations by depth from core sediment samples at the red mud dumping station and evaluated benthic communities in 2004, 2009, 2012, 2017, and 2019. At the dumping station DB-085, the Cr content in the upper layer (0-10 cm) exceeded the effect range median criteria in all study years and decreased with time. Geochemical fraction studies using sequential extraction methods from core sediment samples in 2004, 2009, and 2017 showed high ratios of non-residual fractions (anthropogenic inputs), indicating persistent potential long-term risk after the 2010 ban. Additionally, we confirmed that Thyasira tokunagai, an opportunistic and contamination-stress-resistant species, dominated the study station.

Efficiency Enhancement of Wide Bandgap Lead Perovskite Solar Cells with PTAA Surface-Passivated with Monomolecular Layer from the Viewpoint of PTAA Band Bending.

This report is on the efficiency enhancement of wide bandgap lead halide perovskite solar cells (WBG Pb-PVK PSCs) consisting of FA0.8Cs0.2PbI1.8Br1.2 as the light-harvesting layer. WGB Pb-PVK PSCs have attracted attention as the top layer of all perovskite-tandem solar cells. Poly[bis(4-phenyl) (2,4,6-trimethylphenyl) amine] (PTAA), a conductive polymer, is always used as the hole transporting layer (HTL) for Pb-PVK PSCs. Nevertheless, the hydrophobic surface of the PTAA sometimes destroys the growth of the FA0.8Cs0.2PbI1.8Br1.2 film. On the other hand, the Fermi level of PTAA is not well matched with that of perovskite film. Thus, the PCE of the WBG Pb-based PSCs with PTAA as the HTL was not very high. In this report, the efficiency of the FA0.8Cs0.2PbI1.8Br1.2 is improved by passivating the surface of the PTAA with a monomolecular layer, where the surface becomes hydrophilic, and the band bending of the PTAA layer is improved to cause swift hole collection. Finally, WBG Pb-PVK PSCs (1.77 eV) with 16.52% efficiency are reported.