Z‑Schematic Artificial Leaf Structure for Biosolar Oxyfunctionalization of Hydrocarbons

The natural Z-schematic photosynthesis is a promising catalytic model for solar-to-chemical conversion. Here, we construct a Z-schematic, wireless photoelectrocatalytic (PEC) system (i.e., artificial leaf) for biocatalytic oxyfunctionalization of hydrocarbons. The monolithic leaf structure consists of a tandem photoanode|photocathode configuration that uses sunlight as the sole energy source to drive redox reactions. Under solar light, the ferric oxyhydroxide-coated, molybdenum-doped bismuth vanadate (FeOOH|Mo:BVO) photoanode extracts electrons from H2O electron feedstock and transfers the electrons to the conjugated polyterthiophene (pTTh) photocathode. Meanwhile, the pTTh photocathode absorbs FeOOH|Mo:BVO-filtered light for O2 reduction to H2O2. The in situ generated H2O2 activates unspecific peroxygenases (UPOs) to drive enantioselective C–H oxyfunctionalization (e.g., hydroxylation and epoxidation). Furthermore, we solve HO•-mediated inactivation of UPOs using a cellulose membrane, which increases enzymatic productivity with a benchmark total turnover number of 193 000 among PEC and photocatalytic platforms that trigger UPO-mediated synthesis

Lignin-Induced CaCO₃ Vaterite Structure for Biocatalytic Artificial Photosynthesis

The vaterite phase of CaCO3 exhibits unique characteristics, such as high porosity, surface area, dispersivity, and low specific gravity, but it is the most unstable polymorph. Here, we report lignin-induced stable vaterite as a support matrix for integrated artificial photosynthesis through the encapsulation of key active components such as the photosensitizer (eosin y, EY) and redox enzyme (l-glutamate dehydrogenase, GDH). The lignin-vaterite/EY/GDH photobiocatalytic platform enabled the regeneration of the reduced nicotinamide cofactor under visible light and facilitated the rapid conversion of α-ketoglutarate into l-glutamate (initial conversion rate, 0.41 mM h–1; turnover frequency, 1060 h–1; and turnover number, 39,750). The lignin-induced vaterite structure allowed for long-term protection and recycling of the active components while facilitating the photosynthesis reaction due to the redox-active lignin. Succession of stability tests demonstrated a significant improvement of GDH’s robustness in the lignin-vaterite structure against harsh environments. This work provides a simple approach for solar-to-chemical conversion using a sustainable, integrated light-harvesting system

Data_Sheet_1_Short-term effect of household indebtedness and risk of alcohol use disorder among Korean youth: 2017–2020 longitudinal panel study.docx

BackgroundIn Republic of Korea, household debt has increased recently among young adults, especially during the COVID-19 pandemic. Household debt may potentially lead to numerous outcomes including alcohol use disorder (AUD). The aim of this study was to investigate the relationship between a change in indebtedness and the risk of developing AUD.MethodsA total of 5,091 participants (2,720 men and 2,371 women) were included during a 4-year study period. Indebtedness was divided into four groups: no debt a year ago and at present (group 1), paying off a year’s debt (group 2), newly incurred current debt after a year when there was no debt (group 3), and indebtedness a year ago and at present (group 4). Groups 2, 3, and 4 were also divided into subgroups based on debt characteristics. AUD risk was evaluated by the CAGE scale, and a score of 2 or higher was defined as AUD high risk. Several time-varying socioeconomic and health-related characteristics were adjusted.ResultsParticipants who indicated indebtedness at present (groups 3 and 4) were more likely to be AUD high-risk compared to group 1 in both genders (men: adjusted relative risk [aRR] = 1.031, 95% CI [1.014–1.049] in group 3, aRR = 1.028, 95% CI [1.007–1.050] in group 4; women: aRR = 1.039, 95% CI [1.016–1.163] in group 3, aRR = 1.028, 95% CI [1.007–1.050] in group 4). Even paid-off debt affected the risk of AUD among female participants (aRR = 1.018, 95% CI [1.001–1.034] in group 2). Women whose amount of debt increased for 1 year were more likely to be AUD high-risk compared to group 1. Women showed higher aRR than men for increasing CAGE scores by one unit in all debt subgroups.ConclusionOur research demonstrated a possible link between indebtedness and a heightened risk of AUD. These results underscore the importance of implementing targeted screening and interventions for AUD, particularly among young women who are facing mounting levels of debt.</p

Additional file 1 of Effect of on-site first aid for industrial injuries on healthcare utilization after medical treatment: a 4-year retrospective longitudinal study

Supplementary Table 1 The relationship between on-site first aid and the number of hospitalization and duration of hospitalizatio

Origins of Efficient Perovskite Solar Cells with Low-Temperature Processed SnO₂ Electron Transport Layer

Recently, SnO2 has been noticed as a promising material for electron-transport layer of planar perovskite solar cells. SnO2 layer presents advantages of low-temperature processability and high power-conversion efficiency, and understanding the correlations between the SnO2 properties and device performance will provide a key to realize more efficient perovskite solar cells. Herein, uniform electron-transport layer using SnO2 nanoparticles is fabricated, and the effect of annealing on the solar-cell performance is discussed. Solar cells with low-temperature processed SnO2-nanoparticle layer (below 120 °C or even at room temperature) exhibit desirable short-circuit current, open-circuit voltage, and fill factor with the highest efficiency of 19.0%. Using atomic force microscopy and ultraviolet photoelectron spectroscopy, both great surface uniformity and favorable band alignment of low-temperature processed SnO2 layer have been observed, which are responsible for the device performance. Furthermore, deep electronic-trap states at the SnO2/perovskite interface are investigated via impedance analysis. Compared to the cells processed over 160 °C, low-temperature processed cells exhibit trap states shifting toward the bandedge and reduced trap density, verifying that controlling the interfacial trap states holds a dominance on the open-circuit voltage and is a critical requisite to enable efficient perovskite solar cells. These less-defective solar cells fabricated below 120 °C show high thermal stability, suggesting further commercial applications

Understanding the Trap Characteristics of Perovskite Solar Cells via Drive-Level Capacitance Profiling

Perovskite solar cells (PSCs) are gaining significant interest as the future of photovoltaics owing to their superior performance and cost-effectiveness. Nevertheless, traps in PSCs have emerged as issues that adversely affect the efficiency and stability of the devices. In this study, the methylammonium chloride (MACl) additive and phenyltrimethylammonium iodide (PTMAI) posttreatment were applied to passivate bulk and surface defects. Furthermore, variations of the traps’ quantitative spatial arrangement have been monitored by using the drive-level capacitance profiling (DLCP) analysis. A similar magnitude of trap reduction was observed for the bulk perovskite layer and two interfaces (electron transport layer (ETL)/perovskite and hole transport layer (HTL)/perovskite) with an optimal concentration of the MACl additive. However, the effect of perovskite posttreatment in reducing the trap density was much more noticeable at the HTL/perovskite interface compared to the bulk and ETL/perovskite regions. This observation was reinforced by the outcomes of the 500 h thermal stability tests at 60 °C from seven independent batches, which demonstrated a substantial suppression of trap accumulation, particularly at the HTL/perovskite interface, by an order of magnitude

“Tree to Bone”: Lignin/Polycaprolactone Nanofibers for Hydroxyapatite Biomineralization

Bone contains an organic matrix composed of aligned collagen fibers embedded with nanosized inorganic hydroxyapatite (HAp). Many efforts are being made to mimic the natural mineralization process and create artificial bone scaffolds that show elaborate morphologies, excellent mechanical properties, and vital biological functions. This study reports a newly discovered function of lignin mediating the formation of human bone-like HAp. Lignin is the second most abundant organic material in nature, and it exhibits many attractive properties for medical applications, such as high durability, stability, antioxidant and antibacterial activities, and biocompatibility. Numerous phenolic and aliphatic hydroxyl moieties exist in the side chains of lignin, which donate adequate reactive sites for chelation with Ca2+ and the subsequent nucleation of HAp through coprecipitation of Ca2+ and PO43–. The growth of HAp crystals was facilitated by simple incubation of the electrospun lignin/polycaprolactone (PCL) matrix in a simulated body fluid. Multiple analyses revealed that HAp crystals were structurally and mechanically similar to the native bone. Furthermore, the mineralized lignin/PCL nanofibrous films facilitated efficient adhesion and proliferation of osteoblasts by directing filopodial extension. Our results underpin the expectations for this lignin-based biomaterial in future biointerfaces and hard-tissue engineering

High-Photovoltage Silicon Nanowire for Biological Cofactor Production

Photocathodic conversion of NAD+ to NADH cofactor is a promising platform for activating redox biological catalysts and enzymatic synthesis using renewable solar energy. However, many photocathodes suffer from low photovoltage, consequently requiring a high cathodic bias for NADH production. Here, we report an n+p-type silicon nanowire (n+p-SiNW) photocathode having a photovoltage of 435 mV to drive energy-efficient NADH production. The enhanced band bending at the n+/p interface accounts for the high photovoltage, which conduces to a benchmark onset potential [0.393 V vs the reversible hydrogen electrode (VRHE)] for SiNW-based photocathodic NADH generation. In addition, the n+p-SiNW nanomaterial exhibits a Faradaic efficiency of 84.7% and a conversion rate of 1.63 μmol h–1 cm–1 at 0.2 VRHE, which is the lowest cathodic potential to achieve the maximum productivity among SiNW-sensitized cofactor production

Interfacial Modification and Defect Passivation by the Cross-Linking Interlayer for Efficient and Stable CuSCN-Based Perovskite Solar Cells

The study of the inorganic hole-transport layer (HTL) in perovskite solar cells (PSCs) is gathering attention because of the drawback of the conventional PSC design, where the organic HTL with salt dopants majorly participates in the degradation mechanisms. On the other hand, inorganic HTL secures better stability, while it offers difficulties in the deposition and interfacial control to realize high-performing devices. In this study, we demonstrate polydimethylsiloxane (PDMS) as an ideal polymeric interlayer which prevents interfacial degradation and improves both photovoltaic performance and stability of CuSCN-based PSC by its cross-linking behavior. Surprisingly, the PDMS polymers are identified to form chemical bonds with perovskite and CuSCN, as shown by Raman spectroscopy. This novel cross-linking interlayer of PDMS enhances the hole-transporting property at the interface and passivates the interfacial defects, realizing the PSC with high power-conversion efficiency over 19%. Furthermore, the utilization of the PDMS interlayer greatly improves the stability of solar cells against both humidity and heat by mitigating the interfacial defects and interdiffusion. The PDMS-interlayered PSCs retained over 90% of the initial efficiencies, both after 1000 h under ambient conditions (unencapsulated) and after 500 h under 85 °C/85% relative humidity (encapsulated)

Evolution of the Electronic Traps in Perovskite Photovoltaics during 1000 h at 85 °C

With growing demands on the stability of perovskite photovoltaics against various degradation factors, understanding and controlling the defect characteristics of devices have become the most essential issues to be resolved. In this work, the organometal halide perovskite is modified with a lithium–fluoride ionic passivator that enables highly stable and efficient solar cells with a power-conversion efficiency of over 21%, retaining up to ∼90% after 1000 h at 85 °C. The thermal degradation regressions of the films and devices have been temporally investigated, and the trap density of states has been scrutinized as a function of time. Surprisingly, the electronic traps of the solar cells exhibit exponential relaxations in both the trap densities and energy levels as thermally stressed, and the incorporation of LiF has greatly enhanced this relaxation with the mitigation of the following degradation. It is suggested that LiF not only passivates the initial formation of the traps but also controls their roles and behaviors under the thermal degradation of devices