Ewing sarcoma (EwS) shows a limited clinical response to poly (ADP-ribose) polymerase (PARP) inhibitors (PARPi), despite promising preclinical data. In this study, we compared five PARPi with different PARP-trapping capacities in PDX-derived cell lines and mouse models. Talazoparib, the strongest PARP-trapping agent, showed markedly greater efficacy than olaparib or veliparib. It triggered extensive DNA damage, micronuclei formation, and activation of the cyclic GMP-AMP synthase (cGAS)/stimulator of interferon genes (STING) pathway, leading to robust type I interferon and pro-inflammatory cytokine release, an effect not seen in osteosarcoma. In vivo, talazoparib also reshaped the tumor microenvironment, increasing macrophage infiltration and reducing tumor growth. In vitro, conditioned media from treated EwS cells promoted M0-like macrophage polarization towards an inflammatory M1-like status. These immunostimulatory effects were initiated by tumor-derived interferons and were absent in talazoparib-resistant and olaparib-treated EwS cells, underscoring the importance of the PARP trapping activity of PARPi rather than catalytic inhibition. Combination of talazoparib with exogenous 2'-3'-cyclic GMP-AMP (cGAMP) does not further increase phagocytosis of EwS cells when co-cultured with macrophages, and no additive effects were observed under the tested conditions. Thus, talazoparib is a potent cytotoxic agent with innate immune activation/macrophage-mediated effects, prompting further clinical evaluation in this tumor type.
Defect engineering offers a practical route to control interfacial charge states in polymer-inorganic composites, yet translating this control into optically writable and non-volatile polarization in soft dielectrics remains difficult. Here, we introduce a Polydimethylsiloxane (PDMS)-based composite that can be written by light to form an interfacial polarization state. The design relies on FeTiO3 (FTO) nanoparticles with oxygen-vacancy associated trap states, whose density is tuned by spark plasma sintering to create a trap-rich polymer-oxide interface. Under illumination, photocarriers promote interfacial charge transfer by reducing the effective barrier at the metal-composite contact, producing a rapid rise in interfacial charge accumulation. After the light is removed, a large fraction of the photoexcited electrons becomes immobilized, leaving a residual polarization that relaxes only slowly. We quantify the write-relax behavior using a triboelectric nanogenerator configuration as a sensitive probe of interfacial charge transfer, and we directly visualize the photo-written electrostatic state and its retention by Kelvin probe force microscopy. These results present defect-mediated charge trapping as a materials-level mechanism for light-programmable, long-retention polarization in soft composites, enabling remotely addressable electrostatic interfaces for soft electronic systems.
To avoid iodine dissolution in electrolytes and the resultant shuttle effect in Na-I2 batteries, a chemo-physical synergistic strategy for iodine immobilization is proposed based on a 3D porous compound formulated as Cu3(OH)2V2O7·2H2O (CuVO). After low-temperature annealing, the dehydrated sample, D-CuVO, becomes amorphous, but maintains the original host skeleton. After H2O2-treatment, D-CuVO recovers to the crystalline phase, and the order-disorder conversion is associated with valence variation. After incorporation of iodine, CuI is detected in D-CuVO@I2, and the cycled D-CuVO@I2 can restore to the original crystalline D-CuVO after H2O2-treatment, indicating the reversible transformation of D-CuVO + 1/2 I2 ↔ CuI + Cu-deficient D-CuVO during cycling. This is related to abundant Cu-O-Cu linkages and short Cu ··· Cu distances in D-CuVO, which can stabilize the framework of D-CuVO in the presence of a Cu defect. Furthermore, I- can be reversibly adsorbed/desorbed on the CuI (111) surface. Additionally, a new NaVO3 host phase appears in the discharge process, which originates from partial irreversible intercalation of Na+ into D-CuVO. The inner channel of the NaVO3 host phase can physically accommodate iodine. D-CuVO@I2 shows excellent electrochemical performance in Na-I2 batteries.
The low quantum efficiency of photocatalysts, constrained by their limited solar spectral response and substantial recombination of photo-generated charge carriers, is the primary bottleneck to the scalability of solar-light-mediated photocatalytic mineralization of organic compounds. In the present report, a hybrid material (Ce-Nb2O5/r-GO) has been rationally designed by doping niobium oxide (Nb2O5) with cerium and embedding the resulting material (Ce-Nb2O5) on reduced graphene oxide (r-GO). The intrinsic Nb2O5 and modified Ce-Nb2O5 materials were synthesized by the facile surfactant-free hydrothermal route, and the hybrid Ce-Nb2O5/r-GO was prepared by applying the ultrasonication method. The structural and morphological characteristics, optical response, and charge-carrier (h+-e-) dynamics in the as-designed materials were studied using various characterization techniques. The Ce-Nb2O5/r-GO exhibits the dispersion of Ce-Nb2O5 particles over the r-GO sheets with substantial broadening of optical response, and facilitated charge transport dynamics, owing to the rare-earth metal doping and combining with the conductive framework. The Ce-Nb2O5/r-GO showcased notable photocatalytic performance, investigated by degrading methyl orange (MO), as it exhibited 91.9% MO degradation and 82.7% mineralization (total organic content analysis) under optimized conditions, pH = 6, [MO] = 5 mg L-1, and Ce-Nb2O5/r-GO = 50 mg/100 mL dose, following first-order kinetics (0.033 min-1) with excellent reusability and photostability. The radical-trapping experiment, combined with electron spin resonance (ESR) analysis, validated the generation of HO˙ and ˙O2 -. The substantial photocatalytic performance, significant reusability, and photostability of the designed photocatalyst highlight its promising potential for solar-light-mediated photocatalytic mineralization of organic pollutants.
The carbon-to-nitrogen (C:N) ratio constrains microbial metabolism, yet whether nutrient stoichiometry controls the differential fates of intracellular (iARGs) versus extracellular antibiotic resistance genes (eARGs) remains unknown. This study aimed to test whether C:N ratios approaching the bacterial threshold elemental ratio (TER) would maximize iARG enrichment through a dissolved organic matter (DOM)-extracellular polymeric substance (EPS)-mobile genetic element (MGE) cascade, while eARG dynamics would be governed by physicochemical processes. Cyanobacteria-bacteria co-cultures at four C:N ratios (5:1, 10:1, 20:1, 40:1) were analyzed using shotgun metagenomics, FTICR-MS, 3D-EEM, untargeted metabolomics, and EPS fractionation. C:N = 10:1 produced the highest iARG abundance (65.1 ± 17.4 TPM, mean ± SD) and a 17-fold iARG/eARG ratio, while eARG showed no significant treatment effect (Kruskal-Wallis p = 0.082, treating triplicate subsamples as observations). FTICR-MS revealed the lowest intensity-weighted O/C (0.334), most negative NOSC (-0.67), and highest molecular diversity (8029 formulas) at C:N = 10:1, indicating a uniquely reduced, aliphatic-enriched DOM pool. (Note: FTICR-MS samples were pooled from triplicate subsamples per treatment, yielding one composite per C:N level; these results are therefore descriptive and unreplicated.) EPS polysaccharide/protein ratios peaked at 2.8, correlating with iARG across treatments (ρ=0.91, p < 0.001) but inversely with eARG (ρ=-0.59, p = 0.044). Guanosine (ppGpp precursor) peaked at C:N = 10:1 (ρ=0.75 with iARG) while UDP-glucose was depleted, confirming active EPS biosynthesis. Piecewise structural equation modeling identified a pathway from C:N through DOM, EPS, and MGE to iARG (R²=0.78, Fisher's C p = 0.31), whereas eARG depended on eDNA physicochemical trapping (R²=0.41). These findings provide evidence that nutrient stoichiometry acts as a selective control on ARG partitioning, suggesting that C:N monitoring could be incorporated into eutrophic water ARG risk assessment.
Aedes vexans, a widespread mosquito species in Germany, is a major nuisance pest and a demonstrated or putative vector of numerous pathogens affecting humans and animals. To document its spatial and temporal occurrence, both passive and active mosquito monitoring programmes have been conducted across Germany.Passive monitoring is carried out through the citizen-science project "Mückenatlas", in which volunteers collect and submit mosquito specimens from across the country. All citizen-collected specimens are subsequently identified by professional entomologists. Active monitoring is performed by experts using a variety of standardised entomological methods, including trapping, aspirating and netting adults, as well as sampling larvae and pupae by dipping and sieving. Portions of the resulting dataset have already been used in scientific publications. This data paper presents a comprehensive dataset on the occurrence of Aedes vexans in Germany, comprising 6,422 records collected between 26.04.2011 and 21.11.2023. Of the total occurrence records, 2963 originate from citizen-science contributions, while the remainder derive from active monitoring efforts. The dataset documents 225,565 individual mosquitoes from 2,784 distinct locations.
Sensitive and accurate detection of mycotoxin contaminations is crucial for ensuring safety of herbal medicines. However, their inherent chemical complexity poses significant challenges for reliable method development. Herein, an innovative segmented multi-dimensional liquid chromatography-tandem mass spectrometry (sMD-LC-MS/MS) method was developed for detection of 85 mycotoxins in complex root and rhizome herbs. By integrating multiple heart-cutting, segmented trapping, and dual-mode second-dimension separations, it resolved critical co-elution issues from conventional 1D analysis. Coupled with a simple "dilute-and-shoot" workflow, the system eliminated offline purification, enhancing throughput. Method validation across six representative herbal matrices demonstrated that this "panoramic" strategy significantly outperformed conventional LC-MS/MS method and achieved improvements in qualitative reliability, quantitative accuracy, and detection sensitivity. It provided a systematic solution for high-throughput, highly reliable detection of trace-level, multiclass mycotoxins in challenging herbal matrices.
The clinical challenge of osteoporotic fracture healing is rooted in a hostile local microenvironment characterized by oxidative stress, hypoxia, and acidosis, which stalls regeneration by trapping macrophages in a pro-inflammatory, metabolically crippled state. Herein, we report an intelligent nanocatalytic medicine composed of a pH-responsive calcium-aluminum layered double hydroxide (CaAl-LDH) decorated with a reactive oxygen species (ROS)-responsive manganese oxide (MnOx), denoted as CALM, for orthopedic implantation. This hierarchical system is designed to modulate key features of the "triple threat" microenvironment: the CaAl-LDH backbone dissolves in the local microenvironment to buffer the acidity, while the MnOx scavenges ROS and simultaneously generates therapeutic oxygen. This comprehensive microenvironment modulation supports mitochondrial function and drives the metabolic and phenotypic reprogramming of macrophages from a pro-inflammatory M1 to a pro-reparative M2 state. In a clinically relevant osteoporotic rat fracture model, the CALM coating significantly accelerated bone regeneration. Mechanistically, transcriptomic and protein-level analyses reveal that CALM exerts its immunomodulatory and osteogenic effects by activating the PI3K/Akt/GSK3β signaling pathway. This work presents a metabolically focused, nano-enabled strategy to break the cycle of non-union, offering a promising therapeutic platform for the treatment of osteoporotic fractures.
Left atrial appendage thrombus (LAAT) in non-valvular atrial fibrillation (AF) usually precludes catheter ablation and complicates left atrial appendage occlusion (LAAO). Patients with persistent LAAT despite anticoagulation and heart failure have limited rhythm-control options. To describe the feasibility and safety of Combined Occlusion and Ablation therapy for left atrial appendage Thrombus (COAT), a same-session "thrombus-sealing first" strategy, in selected patients with persistent AF, heart failure, and persistent LAAT despite therapeutic OAC. This single-center retrospective proof-of-concept cohort included five patients who underwent COAT between January 2022 and April 2026. LAAO was performed first using a no-touch thrombus-trapping technique. Catheter ablation was performed after device release, confirmation of device stability and sealing, and absence of neurological abnormality. Follow-up included imaging and rhythm surveillance with electrocardiography and Holter monitoring. All five procedures were completed successfully, with first-attempt device deployment and pulmonary vein isolation in all patients. Sinus rhythm was restored in all patients. No periprocedural stroke, transient ischemic attack, systemic embolism, major bleeding, pericardial tamponade/effusion, device embolization, or death occurred. At a median imaging follow-up of 58 days, TEE confirmed complete LAA sealing without device-related thrombus in four patients; one patient declined TEE and cardiac CTA. The four patients with TEE follow-up were transitioned from anticoagulation to lifelong single antiplatelet therapy (SAPT). No thromboembolic or major bleeding events occurred. Four patients remained arrhythmia-free. In this small, selected proof-of-concept cohort, COAT appeared feasible and was not associated with observed major complications. Larger prospective studies are required.
Hydrogen peroxide (H2O2) is an essential industrial oxidant, yet its conventional production remains energy-intensive and generates hazardous byproducts. Flexocatalysis has emerged as a promising mechanochemical strategy that overcomes the symmetry constraints of piezoelectric materials, allowing a wider range of semiconductors to participate in mechano-driven redox reactions. However, this green approach faces challenges due to inefficient mechanochemical energy conversion and insufficient active sites. In this study, the g-C3N4/SrTiO3 nanocomposites are prepared by initially hydrothermally-synthesizing SrTiO3, which was then mechanically mixed with g-C3N4 and calcined. The optimized heterojunction demonstrates an elevated H2O2 production rate of 645.1 μmol·g-1·h-1 when subjected to ultrasonication, outperforming the yields of pristine g-C3N4 and SrTiO3 by 2.7 and 3.7 folds, respectively. The improved efficiency is attributed to the effective spatial separation of mechano-induced charges across the heterointerface, which suppresses charge recombination and thereby enhances the overall redox efficiency. Mechanistic investigations, including electron spin resonance spectroscopy and radical trapping experiments, collectively demonstrate that the sequential two-step single-electron oxygen reduction serves as the predominant pathway for H2O2 generation. This study highlights the potential of heterojunction engineering in advancing flexocatalytic systems and presents a scalable, sustainable strategy for ultrasound-driven H2O2 synthesis.
Soft-lattice nanocrystal photon management hinges on controlling relaxation branching, diverting excitations from interfacial losses into radiative pathways. CsPbCl3:Yb3+ quantum cutting benchmarks this, but is still constrained by surface trapping, suboptimal Yb-pair branching energetics, and limited thermal/environmental stability. Here we implement a (2-bromoethyl)trimethylammonium bromide (BETAB)-enabled passivation strategy with annealing-triggered gradient halide reconstruction. BETAB replaces OA/OAm to reduce surface losses, while mild annealing activates ligand-associated Br- as a local reservoir to drive Br- in-diffusion with Cl- counter-migration, writing a continuous radial Cl/Br gradient (Br-rich interior). The graded halide landscape suppresses interfacial quenching and creates a radial band-edge bias that funnels excitations into the QC pathway, accelerating exciton-to-Yb3+ transfer. Consequently, QC PLQY increases stepwise from 84.7% (pristine) to 125.4% (BETAB-treated) and 155.2% (annealed). Integrated as spectral-conversion films on Si photodetectors, the treated NCs enable 200-1100 nm detection with responsivity up to 0.5 A W-1, EQE of 64.17%, and D* >1.02 × 1012 Jones (300-1100 nm) and 4.8 × 1011 Jones (200-300 nm), delivering clear ultrabroadband imaging in 7 × 7 arrays. The reconstructed NCs further show ATQ-like behavior (134% at ∼333 K) and improved aging stability (86.1% retention after 60 days vs 29.2% for pristine). Overall, ligand-enabled gradient writing reroutes relaxation for robust photon management.
Vertical stratification has long been recognized as a key dimension of biodiversity in structurally complex ecosystems, shaping animal movement and community structure. Camera traps provide a powerful means to extend biodiversity monitoring across forest strata through continuous, standardized observation. However, most camera trapping studies focus on terrestrial observations or a single arboreal layer, limiting inference about vertically structured communities. Here, we evaluate a standardized "camera column" approach for assessing mammal community occupancy in the Congo Basin. We deployed camera traps in three forest strata (canopy, understory-midstory, and ground) at each sampling point in a standardized grid and used a multispecies, multi-scale occupancy model to assess how incorporating observations across strata influences estimates of species occupancy. Our results demonstrate that incorporating vertical space can alter the inferred relationship between mammal communities and environmental gradients, with a significant positive effect of elevation on mean occupancy emerging only when observations from all forest strata were incorporated. These results suggest that even small elevation gradients in lowland tropical forests can shape mammal diversity, likely through soil-mediated effects on habitat structure and resource availability. Furthermore, accounting for three-dimensional habitat structure may be essential for accurately characterizing community-environment relationships in vertically structured systems.
Perovskite solar cells (PSCs) are currently limited by a critical trade-off between the need for thick absorber layers (1000-1500 nm) to ensure sufficient light absorption and the environmental concerns regarding high lead (Pb) toxicity. While metal-based general light-trapping strategies like plasmonics or surface texturing have been explored, they often involve complex fabrication or offer marginal gains with high reflective loss. In this work, we present a high-performance, lead-reduced strategy using an optimized array of SiO2 dielectric material-based nanospheres which can confine and scatter light with almost zero loss. By embedding a 61 nm diameter three-sphere array 50% into the FTO layer, we achieve significant optical confinement via angular scattering. This mechanism allows a thin 300 nm MAPbI3 layer to achieve a 10.7% enhancement in average absorption, raising the short-circuit current density (J sc) to 29.11 mA cm-2 and the power conversion efficiency (PCE) from 22.58% to 24.61%. Crucially, this architecture enables a 73.78% reduction in lead content without sacrificing performance. This approach provides a scalable and eco-friendly pathway for the development of stable, high-efficiency, and low-toxicity next-generation photovoltaics.
The intravenous delivery of mesenchymal stromal cells (MSCs) is often limited by pulmonary entrapment and poor survival under oxidative stress in inflammatory environments. To overcome these challenges, a multifunctional cell-surface engineering strategy driven by the synergistic coordination of polyethylene glycol (PEG), epigallocatechin gallate (EGCG), and magnesium (Mg2+) was adopted in this study. PEG and EGCG were first covalently coupled to form the polymer, PEG-EGCG, in which PEG provides "stealth" shielding, and EGCG facilitates mild membrane insertion and Mg2+ coordination. The resulting PEG-EGCG-Mg complex self-assembled on MSCs, forming a stealth layer and a metal-phenolic network. This P-E-Mg@MSCs design significantly reduced cell adhesion to endothelium and collagen, thereby diminishing pulmonary trapping and leading to increased bone marrow accumulation in a murine model of immune-mediated aplastic anemia (AA). Furthermore, the coating conferred potent antioxidant and anti-inflammatory properties, thereby improving MSC survival under oxidative stress. In AA mice, treatment with P-E-Mg@MSCs restored peripheral blood counts, reduced bone marrow adiposity, and modulated immune imbalance by upregulating regulatory T cells and downregulating cytotoxic CD8+ T cells, thereby outperforming unmodified MSCs. This work presents a versatile coating platform that integrates adhesion inhibition, microenvironment modulation, and metal-ion coordination to enhance the systemic delivery and therapeutic efficacy of MSCs for regenerative and immunomodulatory applications.
Diffuse idiopathic pulmonary neuroendocrine cell hyperplasia (DIPNECH) is a rare pulmonary precursor lesion that is characterized by the diffuse proliferation of neuroendocrine cells within the airway epithelium. Because obtaining a surgical specimen for histological confirmation is often difficult, management strategies for asymptomatic patients are controversial. It is generally considered an indolent condition that is often managed conservatively. However, diagnosis can be difficult in asymptomatic patients because radiological findings may resemble those of early-stage lung cancer. We present 2 cases of asymptomatic patients with DIPNECH who were detected incidentally during radiological surveillance. High-resolution CT revealed multiple pulmonary nodules in both patients, accompanied by subtle findings indicative of small-airway involvement, such as mosaic attenuation and air trapping. Despite normal laboratory findings, normal pulmonary function tests, and the absence of respiratory symptoms, serial imaging revealed slow but definite enlargement of a dominant pulmonary nodule, making it difficult to exclude malignancy with confidence. The 1st patient was a 63-year-old nonsmoking woman who was observed for multiple pulmonary nodules over 6 years. During this period, a centrally located dominant nodule in the left lower lobe gradually enlarged, prompting a diagnostic left lower lobectomy. In the 2nd case, a 51-year-old nonsmoking woman demonstrated progressive enlargement of a dominant nodule over 2 years, prompting video-assisted thoracoscopic segmentectomy. Histopathological examination in both patients confirmed DIPNECH, allowing for the exclusion of invasive malignancy and a comprehensive pathological assessment of neuroendocrine cell proliferation. These cases illustrate a practical diagnostic challenge in patients with suspected DIPNECH who are asymptomatic. Although radiological surveillance is usually appropriate for indolent disease, the progressive enlargement of a dominant pulmonary nodule can limit the reliability of observation alone. Therefore, surgical resection can be justified as a diagnostic strategy within a multidisciplinary framework when malignancy cannot be confidently excluded, although careful patient selection and long-term surveillance remain essential.
A mild, visible-light-driven protocol has been developed for the regioselective ortho-C(sp2)-H mono-halogenation (Cl, Br, and I) of 3-aryl-2H-benzo[b][1,4]oxazin-2-ones via a synergistic metallaphotoredox strategy. The transformation employs Pd(OAc)2 (20 mol %) in combination with the organic photocatalyst eosin Y (WS, 10 mol %) under irradiation with a 24 W blue LED, using bench-stable N-halo-5,5-dimethylhydantoins (DCDMH, DBDMH, and DIDMH) as sustainable halogen sources. Conducted in 1,2-dichloroethane (DCE) with p-toluenesulfonic acid (1.0 equiv.) as an essential additive, the reaction proceeds under oxidant-free and thermally mild conditions to afford ortho-halogenated products in high isolated yields (75%-97%) with excellent regioselectivity. A broad range of substituents on the 3-aryl ring, including electron-donating, electron-withdrawing, and extended aromatic groups, are well tolerated. Mechanistic investigations-including radical trapping experiments (TEMPO, BHT), light on/off studies, and control reactions-support a cooperative pathway involving Pd(II)-directed C─H activation and photoredox-mediated generation of halogen radicals, followed by radical capture and reductive elimination from high-valent palladium intermediates. This operationally simple dual catalytic approach provides an efficient platform for late-stage diversification of pharmaceutically relevant 2H-benzo[b][1,4]oxazin-2-one scaffolds and advances sustainable strategies in photocatalytic C─H halogenation.
Cerebrovascular surgery has shifted a lot from the microsurgical aspects to the endovascular surgeries in nearly most of the cases. However, there are still some major controversies when one sees the long-term follow-up of microsurgical and endovascular procedures.MC aneurysms, PICA VA junction and PICA aneurysms, IC aneurysms with good cross flow (trapping), revascularisation surgery, dural AVF (coagulation or coiling), ICH evacuation timing, and recent changes in mechanical thrombectomy timing are a few of these examples. This chapter will comprehensively aim to provide an outlook on the best possible modality in these controversial aspects of cerebrovascular surgery.
Paraclinoid aneurysms, arising from the internal carotid artery between the proximal dural ring and the posterior communicating artery, pose significant microsurgical challenges due to their proximity to critical neurovascular structures. Despite advances in endovascular techniques, surgical clipping offers definitive exclusion with lower recurrence. This study evaluates surgical outcomes and operative nuances in clipping paraclinoid aneurysms over a 12-year period. A retrospective review was conducted of 116 patients with paraclinoid aneurysms who underwent surgical clipping at a tertiary centre between 2011 and 2023. Data on demographics, clinical presentation, aneurysm morphology, surgical strategy, and outcomes were analysed. The outcome was assessed using the modified Rankin Scale (mRS), with a favourable outcome defined as mRS 0-2. A p-value < 0.05 was considered significant. Informed consent was obtained from all the patients. Among 116 patients median age at presentation was 48 (38.25-59.75) years, 80.2% presented with subarachnoid haemorrhage (SAH). Most had good preoperative status (Hunt & Hess grade I-II: 63.8%; mRS 0-2: 66.4%). Clipping was performed in 84.5%, with alternative strategies including trapping (8.6%) and wrapping (3.4%). Anterior clinoidectomy was required in 70.7% (intradural: 41.4%, extradural: 29.3%). Intraoperative rupture occurred in 20.7%, and multiple clips were used in 27.6%. Postoperative complications included infarcts (23.3%), vasospasm (32.8%), and seizures (7.8%). At discharge, 58.6% had favourable outcome; mortality was 17.2%, increasing to 23.3% at final follow-up. Visual outcomes were better after extradural clinoidectomy, with improvement in 32.4% versus 4.2% for intradural approach. Microsurgical clipping remains a viable, effective treatment for paraclinoid aneurysms, particularly in younger patients and ruptured cases. Extradural anterior clinoidectomy may confer superior visual outcomes. Despite technical complexity, favourable functional outcomes (mRS 0-2) were achieved in 64.6% of patients, underscoring the continued relevance of surgical management in appropriately selected cases.
Hole transport layer-free perovskite solar cells (HTL-free PSCs) are promising candidates for low-cost and scalable photovoltaic technologies. Yet, their performance is still limited by insufficient light harvesting and imperfect contact energetics. In this work, we focus on carbon-based HTL-free PSCs (C-PSCs) and numerically design and study an architecture that combines a double electron transport layer (DETL), a printable carbon back electrode, and a nanostructured aluminum (Al) rear contact. On the front side, a bilayer electron transport stack is employed to support efficient electron extraction and favorable band alignment with the perovskite absorber. On the rear side, a subwavelength graded Al grating is introduced and decorated with plasmonic Al nanoparticles (NPs) located near the perovskite/carbon interface. Three-dimensional finite-difference time-domain (FDTD) simulations are performed to resolve the optical field distribution and the resulting generation profile in the perovskite layer, enabling us to assess how the nanostructures affect the device photocurrent directly. Adding only the graded Al grating increases the short-circuit current density (JSC) from 16.71 (mA/cm2) for a planar reference device to 23.09 (mA/cm2). When Al NPs are incorporated into the grating, JSC further rises to 23.58 (mA/cm2), and the power conversion efficiency (PCE) improves from 10.09% to 14.41%, while the fill factor (FF) remains close to 81%. Finally, we investigate the role of allowable additives in the printable carbon ink by systematically increasing its work function from 5.0 to 5.5 (eV). This work-function engineering mainly affects the open-circuit voltage, which increases from 0.743 to 1.08 (V), whereas JSC remains nearly constant at about 23.7 (mA/cm2). As a result, the PCE increases from 10.09% to 21.61%, with a maximum FF of 84.26%. Overall, the results indicate that combining a double electron transport layer with Al-based nanophotonic light trapping and additive-assisted work-function tuning of carbon electrodes provides a promising route toward high-efficiency HTL-free C-PSCs.
This study aims to enhance singlet oxygen (1O2) generation in visible-light-driven photocatalytic systems through photosensitizer structural regulation and heterojunction engineering. Polyazene zinc phthalocyanine (ZnPPc) was synthesized and coupled with bismuth oxychloride (BiOCl) to construct a BiOCl/ZnPPc composite photocatalyst with a proposed Z-scheme charge transfer pathway. BiOCl/ZnPPc exhibited excellent photocatalytic degradation performance toward the electron-rich antibiotic chlorotetracycline (CTC), with an apparent degradation rate constant of 0.108 min-1, which was nearly one order of magnitude higher than that of pristine BiOCl (0.011 min-1). Reactive species trapping experiments and EPR analysis confirmed that 1O2 was the dominant reactive species, contributing up to 72% to CTC degradation. Photoelectrochemical measurements, PL/phosphorescence analysis, and DFT calculations further revealed that BiOCl/ZnPPc promotes 1O2 generation through the synergistic contribution of energy transfer and Z-scheme interfacial charge transfer pathways. The porous polymeric structure of ZnPPc alleviates the π-π stacking of monomeric ZnPc and facilitates singlet/triplet exciton generation, thereby enhancing 1O2 production via the energy transfer pathway. Meanwhile, the interfacial electronic coupling, built-in electric field, and charge redistribution between BiOCl and ZnPPc promote charge separation and migration, supporting 1O2 generation through the electron transfer pathway. In addition, BiOCl/ZnPPc showed good environmental adaptability and cycling stability, while degradation pathway identification, and toxicity assessment indicated that CTC was mainly transformed into less toxic intermediates with partial mineralization under the present reaction conditions. This work provides a feasible strategy for constructing photosensitizer-based heterojunction photocatalysts capable of efficient 1O2 generation for antibiotic pollutant degradation.