Two-dimensional (2D) Ruddlesden-Popper perovskites (RPPs), which possess a strong quantum confinement effect, have been demonstrated to exhibit out-of-plane charge transport, but the factors that determine the interlayer charge transport in 2D RPPs are far from being explored. In this study, using a recently developed ab initio simulation method which combines density functional theory calculations, semiclassical Marcus theory, and Einstein relationship, we systematically investigate the out-of-plane charge mobilities by focusing on the 2D RPPs with different organic spacers and stacking patterns of the inorganic sublattice. It is found that regardless of the organic species, the arrangement of neighboring inorganic layers can significantly manipulate the reorganization energies when the charge carriers are spatially localized in the inorganic flakes, while the electronic couplings between inorganic layers are weakly affected in 2D RPPs. Resultantly, the out-of-plane charge mobilities are enhanced 1-2 orders of magnitude when the inorganic sublattice displays the configuration with adjacent inorganic sheets showing up-to-down alignment in the 2D RPPs. These findings provide novel insights toward designing 2D RPPs with boosted out-of-plane charge transport when carrier localization occurs in the inorganic sheets of the 2D RPPs.

Hybrid lead halide perovskites have emerged as versatile candidates for advanced optoelectronic applications. However, precise control over their phase interconversion remains challenging. Here, we report two structurally distinct 2D perovskites, S-[BPEA]2PbI4 and rac-[BPEA]2PbI4, featuring near Dion-Jacobson (nDJ) and near Ruddlesden-Popper (nRP) stacking configurations induced by stereospecific organic cations. Under mild hydrostatic pressure, both compounds exhibit significant photoluminescence enhancement (1.97 times at 0.38 GPa, 1.09 times at 0.22 GPa) and tunable emission energies. Notably, S-[BPEA]2PbI4 undergoes a nDJ-to-nRP phase transition, while rac-[BPEA]2PbI4 evolves toward an ideal RP phase, driven by supramolecular interaction modulation and octahedral distortion. In addition, structural analyses, including Hirshfeld surface mapping, deformation potential modeling, and in situ high-pressure PXRD, quantitatively correlate lattice response with emission behavior. Moreover, both materials exhibit reversible mechanochromic luminescence, underscoring their mechanical robustness and optical responsiveness. These findings establish a supramolecular engineering framework for controlling phase structure and light emission in 2D hybrid perovskites via pressure stimuli, enabling their future use in optoelectronic systems.

Two-dimensional (2D) perovskites are promising for optoelectronic applications; however, a fundamental understanding of how organic spacer cations govern vertical charge transport remains elusive. Here, we employ a first-principles framework that combines ab initio molecular dynamics, projection-operator diabatization, and semiclassical Marcus theory to elucidate the effect of spacer cation isomerism. We show that isomerization of the carbon backbone from linear 𝑛-butylammonium to branched iso-butylammonium significantly enhances out-of-plane charge transfer rates and carrier mobilities. This enhancement originates from a synergistic interplay between interlayer spacing and dynamic structural fluctuations. The branched spacer shortens the effective carbon chain, leading to decreased interlayer separation and an increase in interlayer electronic coupling. Meanwhile, weaker hydrogen-bonding interactions between the spacer cation and the inorganic framework induce enhanced thermal fluctuations of the Pb–Br lattice, resulting in stronger diabatic energy level fluctuation and only a moderate increase in reorganization energy. Consequently, the gain in electronic coupling outweighs the increase in reorganization energy, yielding substantially higher Marcus charge transfer rates in the branched spacer system. These findings reveal carbon-chain isomerism as a key design strategy for promoting interlayer charge transport and provide guiding principles for the development of high-performance 2D perovskite optoelectronic materials.

The performance of kesterite Cu2ZnSnS4 (CZTS) solar cells is limited by severe open-circuit voltage losses arising from defect-mediated nonradiative recombination. Using ab initio nonadiabatic molecular dynamics simulations, we elucidate how oxygen and sodium jointly regulate sulfur-vacancy-induced charge recombination at the atomistic level. Doubly positively charged sulfur vacancies induce outward relaxation of neighboring Sn cations, creating deep donor-like trap state through enhanced antibonding Sn-5s/S-3p hybridization and dramatically reducing carrier lifetime. Under oxygen-poor conditions, atomic oxygen passivates sulfur vacancies by restoring local tetrahedral coordination, eliminating deep traps, and extending carrier lifetimes by approximately 3-fold. In contrast, under oxygen-rich conditions, molecular oxygen dissociation produces interstitial oxygen that introduces mid-gap states via antibonding Cu-3d/O-2p interactions, accelerating recombination to subnanosecond time scales. Sodium stabilizes oxygen configurations by forming Na-O complexes, suppresses Cu-O antibonding, and restores carrier lifetimes to near-pristine values. These findings establish general principles for rational defect passivation in kesterite photovoltaics.

OBJECTIVES:This economic evaluation aimed to identify a cost-effective first-line treatment for unresectable hepatocellular carcinoma (uHCC) within China's healthcare system, specifically focusing on immune checkpoint inhibitor (ICI)-based regimens relevant to clinical practice, including newly approved options. METHODS:Relative efficacy was synthesized from six phase III trials forming a star-shaped network with sorafenib as the common comparator, using a Bayesian network meta-analysis with Royston-Parmar models, accounting for non-proportional hazards. A 10-year, three-state partitioned survival model estimated discounted (5% annually) costs and quality-adjusted life-years (QALYs). Sensitivity analyses tested structural and parameter uncertainty. RESULTS:After discounting, camrelizumab-rivoceranib provided more QALYs at a lower cost than three other ICI-based combinations (anlotinib-penpulimab, sintilimab-bevacizumab biosimilar, and toripalimab-bevacizumab), establishing strict dominance. The incremental cost per QALY gained was $10,715 for tislelizumab versus sorafenib, $56,796 for camrelizumab-rivoceranib versus tislelizumab, and $294,795 for atezolizumab-bevacizumab versus camrelizumab-rivoceranib. All findings remained robust in sensitivity analyses. CONCLUSIONS:For uHCC in China, tislelizumab represents a cost-effective choice at the current willingness-to-pay threshold of $40,344 per QALY (3×gross domestic product (GDP) per capita). This analysis provides timely evidence to inform clinical practice and policy decisions regarding the allocation of finite healthcare resources.

Tailoring passivators to modulate surface defects of perovskite films represents a pivotal approach to simultaneously improving the optoelectronic properties and long-term operational stability of perovskite solar cells (PSCs). The design of passivators that simultaneously achieve surface passivation and charge extraction is particularly crucial. Herein, we report a dual-site synergistic passivation material, 1-naphthalenethylamine iodide (NEAI1), which is low-cost, structurally simple, and has π-π regulatory effects. It is incorporated into the interfacial passivation layer between the perovskite films and the hole transport layer (HTL). Theoretical calculations show that NEAI1 with naphthalene conjugated structure exhibits stronger electron delocalization ability and larger molecular dipole moment, which can effectively induce interfacial charge transfer. Therefore, NEAI1 showed a champion power conversion efficiency (PCE) of 25.33% and still retained 93.47% of the initial value after storage for about 2200 h, demonstrating excellent device stability. In addition, NEAI1 effectively reduces losses caused by perovskite defects by coordinating with uncoordinated Pb2+ and compensating for iodine vacancies through a dual-site synergistic passivation mechanism.

Tailoring the self-assembled monolayer (SAM)/perovskite interface is an effective approach to enhance hole-extraction in p-i-n structured perovskite solar cells (PSCs). However, the co-SAM strategy faces the challenge of competing anchor sites, which can interfere with the intended function of the original SAM. In this study, a fluorination strategy is used to design and synthesize a dual-functionalized interfacial material, [2,3,5,6-tetrafluoro-4-(trifluoromethyl) phenyl] phosphonic acid (FPA). Multiple active sites in FPA not only compensate for the anchoring deficiencies of the SAM but also effectively passivate the buried defects of the perovskite through coordination and hydrogen bonding, thereby effectively mitigating both deep and shallow defects at the SAM/perovskite interface. Ultimately, the efficiency of the best-performing solar cells increases from 23.38% of the control device to 25.08% of the modified devices. In parallel, the unencapsulated devices retain over 90% of its initial efficiency after aging 1000 h at RH (65 +/- 5)% in air at (25 +/- 5) degrees C. The study provides an important approach in regulating the SAM/perovskite interface for enhanced charge extraction and environmental stability of the PSCs.

Passivating detrimental defects is essential for improving perovskite solar cells (PSCs) performance. While hydrogen interstitials are often considered harmful, their role in defect passivation remains unclear. Using ab initio nonadiabatic molecular dynamics, we uncover a self-passivation mechanism between hydrogen (Hi-1) and bromine (Bri+1) interstitials in all-inorganic CsPbBr3 perovskites. The Bri+1 defect forms a Br3- trimer that creates a deep trap state, causing rapid charge recombination within tens of nanoseconds. The isolated Hi-1 defect, adopting a Pb-H-Pb bridging configuration, accelerates nonradiative recombination by enhancing thermal disorder and nonadiabatic coupling. However, the Bri+1/Hi-1 complex disrupts the Br3- trimer and restores the local coordination, eliminating the deep trap and extending the carrier lifetime to tens of microseconds. The improvement arises from symmetry breaking, vibrational anharmonicity, and longitudinal Br displacements that localize the band edge states. Our results reveal an intrinsic self-passivation pathway and provide microscopic insight into hydrogen-assisted stability in PSCs.

The continuous demand for lithium-ion batteries (LIBs) in consumer products and electric vehicles (EVs) has raised concerns about their environmental impact when not disposed of properly. Among the components of a spent LIB, the recovery of heavy metals such as Nickel, Manganese, and Cobalt from the cathode materials is the most critical. While this goal can be achieved through processes such as biohydrometallurgy, it relies on large quantities of chemicals such as FeSO4 for the energy source, which can limit the scalability. In this work, we seek to develop a modified biohydrometallurgy process that is self-sufficient. For this purpose, we examined the feasibility of replacing FeSO4 salt with metallic Fe, which is readily available and abundant in spent batteries as protective cases. The growth profile of the autotrophic bacterium Acidithiobacillus ferrooxidans (Atf) was studied after the initial acidification with H2SO4 or HCl. The resulting culture was then used to leach model cathode materials made of NMC622 (Ni:Mn:Co=6:2:2). Near-unity leaching efficiencies were measured on all four elements of interest, Li, Ni, Mn, and Co, when compared with those by aqua regia based digestion. This new bioleaching process opens the door to efficiently recovering cathode metals while further simplifying the cultivation process, promising scaled up applications.

Multicarbon (Cn, where n ≥ 2) oxygenates are important industrial precursors that can be synthesized from the coupling of simple and abundant C1 feedstock such as CH4. While C2 products from this route have been reported, those involving the direct coupling of more than two C1 precursors are rare. As a proof of concept, here we report the synthesis of acetone (CH3COCH3) through the direct coupling of two CH4 and one CO using a combined photothermocatalytic approach. With TiO2 as a light absorber and Pd nanoparticle as a cocatalyst, CH4 activation and subsequent coupling with CO were achieved at 10 bar and 150 °C. A high selectivity of acetone formation among all liquid products (>80%) was measured. Experiments with isotope-labeled precursors confirmed that the product was a result of the direct coupling of CH4 and CO. The other major liquid product was acetic acid (CH3COOH), which was a result of a single coupling between CH4 and CO. The suitable binding strength between Pd and the reactive intermediates was proposed as a key reason for the high selectivity toward C3 products.

The oxygen evolution reaction often limits the efficiency of renewable fuel syntheses due to its sluggish reaction kinetics. Of the factors that have been studied to improve this important reaction is how the choice of the electrolyte may alter the reaction kinetics. Despite its importance, systematic studies of this effect have been relatively rare. Herein, we report an effort toward correcting this deficiency by investigating the effect of nitrate on water oxidation catalyzed by IrOx. The results show that nitrate can suppress the reaction, resulting in a decrease in the rate and an increase in the Tafel slope. The effect was found to be consistent with a microkinetic model incorporating competitive adsorption between reaction intermediates and nitrate, suggesting that the reaction mechanism was unaffected by the anion identity. Moreover, this blocking effect exhibited dependence on the cations, following a trend of Li+ approximate to Na+ approximate to K+ > Cs+ > TEA(+). The results are expected to have broad applications in electrocatalysis.

Electrocatalytic nitrate reduction reaction (NO3RR) represents a sustainable and environmentally benign route for ammonia (NH3) synthesis. However, NO3RR is still limited by the competition from hydrogen evolution reaction (HER) and the high energy barrier in the hydrogenation step of nitrogen-containing intermediates. Here, we report a selective etching strategy to construct RuM nanoalloys (M = Fe, Co, Ni, Cu) uniformly dispersed on porous nitrogen-doped carbon substrates for efficient neutral NH3 electrosynthesis. Density functional theory calculations confirm that the synergic effect between Ru and transition metal M modulates the electronic structure of the alloy, significantly lowering the energy barrier for the conversion of *NO2 to *HNO2. Experimentally, the optimized RuFe-NC catalyst achieves 100% Faraday efficiency with a high yield rate of 0.83 mg h(-1) mg(cat)(-1) at a low potential of - 0.1 V vs. RHE, outperforming most reported catalysts. In situ spectroscopic analyses further demonstrate that the RuM-NC effectively promotes the hydrogenation of nitrogen intermediates while inhibiting the formation of hydrogen radicals, thereby reducing HER competition. The RuFe-NC assembled Zn-NO3- battery achieved a high open-circuit voltage and an outstanding power density and capacity, which drive selective NO3- conversion to NH3. This work provides a powerful synergistic design strategy for efficient NH3 electrosynthesis and a general framework for the development of advanced multi-component catalysts for sustainable nitrogen conversion.

Pb vacancies slow down hot carrier cooling dynamics in MAPbI 3 perovskites by introducing intraband states that can trap holes and by decreasing the deformation of the [PbI 6 ] 4− octahedron, which leads to weakened electron–phonon coupling.

>Photoelectrochemical (PEC) overall water splitting (OWS) represents a highly promising strategy to directly harvest solar energy and store it in the form of fuels,offering unique benefits such as mitigating issues connected to the intermittent nature of sunlight.

Photocatalytic oxidative coupling of methane (OCM) to ethane promises a route to value-added C-2 products from an abundant and low-cost feedstock. However, selective activation of the C-H bond of CH4 without overoxidation to CO2 has been a major challenge. In this work, we present the use of Au-modified Bi2WO6 as a prototypical photocatalyst, demonstrating a high performance of OCM through photocatalysis. A C2H6 production rate at 1.69 x 10(3) mu molg(-1)h(-1) with approximately 85% selectivity was achieved, which ranks among the top-performing photocatalytic OCM systems. Efforts were also made in establishing a correlation between improved OCM performance and the photocatalyst system by examining the nature of the oxide photocatalyst. Our findings indicated that oxygen within the oxide surface, likely from adsorbed and subsequently dissociated oxygen at the vacancy sites, afforded a desired reactivity to selectively activate the C-H bond without significant overoxidation. Surprisingly, it was revealed that the Au cocatalyst plays dual roles of activating the oxide photocatalyst for enhanced CH4 activation and promoting C-C coupling to yield C2H6 as the main product.

BackgroundPolycystic ovary syndrome (PCOS) is a heterogeneous metabolic and endocrine disorder that causes anovulatory infertility and abnormal folliculogenesis in women of reproductive age. Several studies have revealed inflammation in PCOS follicles, and recent evidence suggests that Berberine (BBR) effectively reduces inflammatory responses in PCOS, however, the underlying mechanisms remain unclear.PurposeTo determine the underlying mechanisms by which BBR alleviates inflammation in PCOS.Study designPrimary human GCs from healthy women and women with PCOS, and KGN cells were used for in vitro studies. ICR mice were used for in vivo studies.MethodsGene expression was measured using RT-qPCR. HAS2, inflammatory cytokines, and serum hormones were assayed by ELISA. Protein expression profiles were assayed by Western blot. Chronic low-grade inflammatory mouse models were developed by intraperitoneal injection with LPS, and PCOS mouse models were established by subcutaneous intraperitoneal injection of DHEA. BBR and 4-MU were administered by gavage. Ovarian morphologic changes were evaluated using H&E staining. HAS2 expression in the ovary was assayed using Western blot and immunohistochemistry.ResultsOur results confirmed that HAS2 expression and hyaluronan (HA) accumulation are closely associated with inflammatory responses in PCOS. Data obtained from in vitro studies showed that HAS2 and inflammatory genes (e.g., MCP-1, IL-1β, and IL-6) are significantly upregulated in PCOS samples and LPS-induced KGN cells compared to their control groups. In addition, these effects were reversed by blocking HAS2 expression or HA synthesis using BBR or 4-MU, respectively. Furthermore, HAS2 overexpression induces the expression of inflammatory genes in PCOS. These results were further confirmed in LPS- and DHEA-induced mouse models, where inflammatory genes were reduced by BBR or 4-MU, and ovarian morphology was restored.ConclusionsOur results define previously unknown links between HAS2 and chronic low-grade inflammation in the follicles of women with PCOS. BBR exerts its anti-inflammatory effects by down-regulating HAS2. This study provides a novel therapeutic target for alleviating ovarian inflammation in women with PCOS.

Two-dimensional lead-halide perovskites provide a more robust alternative to three-dimensional perovskites in solar energy and optoelectronic applications due to increased chemical stability afforded by interlayer ligands. At the same time, the ligands create barriers for interlayer charge transport, reducing device performance. Using a recently developed ab initio simulation methodology, we demonstrate that ligand fluorination can enhance both hole and electron mobility by 1-2 orders of magnitude. The simulations show that the enhancement arises primarily from improved structural order and reduced thermal atomic fluctuations in the system rather than increased interlayer electronic coupling. Arising from stronger hydrogen bonding and dipolar interactions, the higher structural stability decreases the reorganization energy that enters the Marcus formula and increases the charge transfer rate. The detailed atomistic insights into the electron and hole transfer in layered perovskites indicate that the use of interlayer ligands that make the overall structure more robust is beneficial simultaneously for chemical stability and charge transport, providing an important guideline for the design of new, efficient materials.

Additive engineering plays a vital role in enhancing perovskite solar cells (PSCs) by passivating defects within the perovskite films. Carboxyl and ester groups are commonly used for their strong binding with under-coordinated Pb2+ ions. However, the impact of additive acidity on the long-term stability of PSCs remains unclear. This study investigates the functional roles of 4-amino-3,5-difluorobenzoic acid (DFAB-A) and methyl 4-amino-3,5-difluorobenzoate (DFAB-AM), which could effectively passivate the film defects. However, the acidity resulting from carboxyl deprotonation in DFAB-A negatively impacts the structural stability of the perovskites. In contrast, DFAB-AM with its ester functionality forms stronger and more stable bonds, contributing to improved passivation and stability. PSCs incorporating DFAB-AM achieve a high power conversion efficiency of 22.51% and maintain 84.3% of their initial efficiency after 800 h of maximum-power-point operation. These findings underscore the importance of carbonyl group design in developing molecular additives to enhance both the efficiency and the durability of PSCs.

As a vital process for solar fuel synthesis, water oxidation remains a challenging reaction to perform using durable and cost-effective systems. Despite decades of intense research, our understanding of the detailed processes involved is still limited, particularly under photochemical conditions. Recent research has shown that the overall kinetics of water oxidation by a molecular dyad depends on the coordination between photocharge generation and the subsequent chemical steps. This work explores similar effects of heterogeneous solar water oxidation systems. By varying a key variable, the reaction temperature, we discovered distinctly different behaviors on two model systems, TiO2 and Fe2O3. TiO2 exhibited a monotonically increasing water oxidation performance with rising temperature across the entire applied potential range, between 0.1 and 1.5 V vs the reversible hydrogen electrode (RHE). In contrast, Fe2O3 showed increased performance with increasing temperature at high applied potentials (>1.2 V vs RHE) but decreased performance at low applied potentials (<1.2 V vs RHE). This decrease in performance with temperature on Fe2O3 was attributed to an increased level of electron-hole recombination, as confirmed by intensity-modulated photocurrent spectroscopy (IMPS). The origin of the differing temperature dependences on TiO2 and Fe2O3 was further ascribed to their different surface chemical kinetics. These results highlight the chemical nature of charge recombination in photoelectrochemical (PEC) systems, where surface electrons recombine with holes stored in surface chemical species. They also indicate that PEC kinetics are not constrained by a single rate-determining chemical step, highlighting the importance of an integrated approach to studying such systems. Moreover, the results suggest that for practical solar water splitting devices higher temperatures are not always beneficial for reaction rates, especially under low driving force conditions.

BACKGROUND:This work was designed to assess the cost-effectiveness of front-line tislelizumab plus chemotherapy (TIS+Chemo) in advanced gastric cancer (GC) or gastroesophageal junction cancer (GEJC) with positive expression of programmed cell death ligand 1 (PD-L1) from the perspective of Chinese healthcare system. RESEARCH DESIGN AND METHODS:A 10-year partitioned survival model was undertaken utilizing clinical data from RATIONALE 305. Costs and utilities were both discounted at an annual rate of 5%. The primary outcome was incremental cost-effectiveness ratios (ICERs) and calculated as the cost per quality-adjusted life years (QALYs). The willingness-to-pay (WTP) threshold was set as $18,625/QALY. Only direct medical costs were considered. Sensitivity analyses and subgroup analyses were performed to evaluate the robustness of the model. RESULTS:In the base-case analysis, the incremental cost and effectiveness associated with TIS+Chemo vs Chemo was 7,361 and 0.38 QALYs, respectively, leading to an ICER of 19,371/QALY. At the WTP threshold of $18,625/QALY, the TIS+Chemo was not a cost-effective first-line treatment option. The model outcomes were robust. CONCLUSIONS:TIS+Chemo did not provide a cost-effective approach for PD-L1 positive advanced GC/GEJC in China setting. However, TIS+Chemo might be cost-effective in provinces with higher WTP threshold. CLINICAL TRIAL REGISTRATION:RATIONALE 305, www.clinicaltrials.gov, identifier is NCT03777657.