CSE triggers ferroptosis via SIRT4-mediated GNPAT deacetylation in the pathogenesis of COPD.

BACKGROUND: It is now understood that ferroptosis plays a significant role in the progression of chronic obstructive pulmonary disease (COPD) induced by cigarette smoke extract (CSE). However, the mechanisms underlying this relationship remain largely unclear. METHODS: In this study, we established a COPD mouse model through exposure to cigarette smoke particulates, followed by H&E staining, analysis of bronchoalveolar lavage fluid, and immunohistochemistry assay. A549 cells were exposed to increasing concentrations of CSE, with the addition of the ferroptosis activator erastin or the inhibitor Fer-1. Cell viability, LDH (lactate dehydrogenase) release, inflammatory cytokines, total ROS (reactive oxygen species), and lipid ROS were measured using the corresponding assay kits. The acetylation level of GNPAT was determined through immunoprecipitation. We assessed the expression levels of molecules involved in plasmalogen biosynthesis (FAR1, AGPS, and GNPAT), GPX4, and SIRT4 using quantitative real-time PCR, western blot analysis, and immunofluorescence staining. RESULTS: CSE-induced lung tissue damage was initially observed, accompanied by oxidative stress, ferroptosis, and increased plasmalogen biosynthesis molecules (FAR1, AGPS, and GNPAT). CSE also induced ferroptosis in A549 cells, resulting in reduced cell viability, GSH, and GPX4 levels, along with increased LDH, ROS, MDA (malondialdehyde) levels, oxidized lipids, and elevated FAR1, AGPS, and GNPAT expression. Knockdown of GNPAT mitigated CSE-induced ferroptosis. Furthermore, we found that CSE regulated the acetylation and protein levels of GNPAT by modulating SIRT4 expression. Importantly, the overexpression of GNPAT countered the inhibitory effects of SIRT4 on ferroptosis. CONCLUSIONS: Our study revealed GNPAT could be deacetylated by SIRT4, providing novel insights into the mechanisms underlying the relationship between CSE-induced ferroptosis and COPD.

Directional Defect Management in Perovskites by In Situ Decomposition of Organic Metal Chalcogenides for Efficient Solar Cells.

Directional defects management in polycrystalline perovskite film with inorganic passivator is highly demanded while yet realized for fabricating efficient and stable perovskite solar cells (PSCs). Here, we develop a directional passivation strategy employing a two-dimensional (2D) material, Cu-(4-mercaptophenol) (Cu-HBT), as a passivator precursor. Cu-HBT combines the merits of the targeted modification from organic passivator and excellent stability offered by inorganic passivator. Featuring with dense organic functional motifs on its surfaces, Cu-HBT has the capability to "find" and fasten to the Pb defect sites in perovskites through coordination interactions during a spin-coating process. During subsequent annealing treatment, the organic functional motifs cleave from Cu-HBT and convert in situ into p-type semiconductors, Cu2 S and PbS. The resultant Cu2 S and PbS not only serve as stable inorganic passivators on the perovskite surface, significantly enhancing cell stability, but also facilitate efficient charge extraction and transport, resulting in an impressive efficiency of up to 23.5 %. This work contributes a new defect management strategy by directionally yielding the stable inorganic passivators for highly efficient and stable PSCs.

Lead-Doped Titanium-Oxo Clusters as Molecular Models of Perovskite-Type PbTiO3 and Electron-Transport Material in Solar Cells.

In this work we have successfully prepared two lead-doped titanium-oxo clusters with core structures that resemble isolated perovskite PbTiO3 species. In the obtained highly symmetric Pb8 Ti7 -oxo cluster, the central TiO6 octahedra are orthogonally extended to adjacent octahedra through corner-sharing and the eight dopant lead ions form a cubic arrangement, making it the first molecular model of perovskite PbTiO3 . Moreover, the clusters readily dissolved in chloroform and showed high solution stability, as confirmed by MALDI-TOF MS measurements. Based on such solution processability, they can be easily spin-coated to form homogeneous films, which were employed as electron-transport materials in perovskite solar cells to give an average power conversion efficiency of around 15 % and improved device stability. This newly developed bottom-up cluster assembly method provides an efficient approach to the construction of atomically precise models of perovskite metal oxides as well as potential molecular tools to extend their applications.

Monoammonium Porphyrin for Blade-Coating Stable Large-Area Perovskite Solar Cells with >18% Efficiency.

Efficient control of crystallization and defects of perovskite films are the key factors toward the performance and stability of perovskite solar cells (PSCs), especially for the preparation of large-area PSCs devices. Herein, we directly embedded surfactant-like monoammonium zinc porphyrin (ZnP) compound into the methylammonium (MA+) lead iodide perovskite film to blade-coat large-area uniform perovskite films as large as 16 cm2. Efficiency as high as 18.3% for blade-coating large-area (1.96 cm2) PSCs with ZnP was unprecedentedly achieved, while the best efficiency of fabricated small-area (0.1 cm2) device was up to 20.5%. The detailed analyses demonstrated the functions of ZnP in crystallization control and defects passivation of perovskite surfaces and grain boundaries. As a consequence, the ZnP-encapsulated devices retained over 90% of its initial efficiency after 1000 h with a humidity of about 45% at 85 °C. This research presents a facile way to achieve the synergistic effect of large-area coating, morphology tailoring, and defect suppression based on the molecular encapsulation strategy for perovskite films, further improving the photovoltaic performance and stability of PSCs.

Efficient Grain Boundary Suture by Low-Cost Tetra-ammonium Zinc Phthalocyanine for Stable Perovskite Solar Cells with Expanded Photoresponse.

Defects within the grain boundaries (GBs) of halide perovskite films make fabrication of efficient and stable perovskite solar cells (PSCs) highly challenging. Here, a low-cost tetra-ammonium zinc phthalocyanine (ZnPc) was used to post-treat the MAPbI3 (MA = CH3NH3) film. Two-dimensional (ZnPc)0.5MA n-1Pb nI3 n+1 was successfully constructed within the GBs of MAPbI3 film achieving a GBs suture for passivating the defects in GBs. Time-resolved photoluminescence showed that the modification increased the decay time from 44 to 57 ns indicating the passivation of GBs reduces trap-assisted recombination. The PSCs with modified perovskite exhibited increased photovoltage, and the best efficiency was improved up to 20.3%. More importantly, the long-term stability of the responding PSCs against humidity and heating was further improved unprecedentedly. Moreover, the modified MAPbI3 films revealed a self-repairing capability under mild heating. This work provided a novel insight into ongoing fabrication of efficient and stable PSCs by the efficient GBs suture with low-cost phthalocyanine.

Effects of polyurethane microplastics combined with cadmium on maize growth and cadmium accumulation under different long-term fertilisation histories.

Agricultural production uses different types of fertilisation treatments, typically employing the combined application of organic fertiliser (OF) or organic-inorganic fertiliser (OIF) to improve soil quality. When coupled with cadmium (Cd), microplastics (MPs) affect plant growth and Cd accumulation in soils treated with different fertilisers. This study systematically examined the effects of polyurethane (PU) MPs coupled with Cd on the growth characteristics, root metabolite characteristics, rhizosphere bacterial community structure, and Cd bioavailability of maize under different long-term fertilisation treatments and soil types (red/cinnamon soil). The combined effects of PU MPs and Cd on maize growth differed across fertilisation treatments. Under OF, maize plants accumulated more Cd than under OIF. The accumulation of Cd in maize plants in red soil was twice that in cinnamon soil. Under OF, PU MPs promoted Cd activation by decreasing the soil pH, while root metabolites promoted Cd adsorption sites by synthesising specific amino acids, degrading aromatic compounds, and synthesising pantothenic acid and coenzyme A. Under OF, PU MPs can lower the soil pH to promote the activation of cadmium, while root metabolites promote root growth and increase cadmium adsorption sites by synthesizing specific amino acids, degrading aromatic compounds, and synthesizing pantothenic acid and coenzyme A, hereby promoting root Cd absorption. Under OIF, PU MPs act by influencing the biosynthesis of amino acids in root metabolites, enriching energy metabolism pathways, promoting the transport and translocation of mineral nutrients, thereby amplifying the "toxic effects" of Cd. This study provides new insights into the risk assessment of PU MPs and Cd coupling under different fertilisation treatments, and suggests that the prevention and control of combined PU MPs and Cd pollution in red soil under OF treatment should receive more attention in the future.

Microplastics promoted cadmium accumulation in maize plants by improving active cadmium and amino acid synthesis.

Combined pollution from microplastics (MPs) and cadmium (Cd) can influence soil environment and soil biota, altering plant growth and development, and Cd mobilization. We investigated the effects of polystyrene (PS) and polypropylene (PP) MPs alongside Cd on soil Cd bioavailability, rhizosphere soil metabolomics, bacterial community structure, and maize (Zea mays L.) growth in two soil types (red soil and cinnamon soil). Although the addition of PS/PP-Cd promoted Cd accumulation in maize plants overall, there were large-particle-size- and small-particle-size-dependent effects in the red soil and cinnamon soil, respectively. The difference is mainly due to the capacity of the large particle size MPs to significantly reduce soil pH, improve soil electrical conductivity (EC), promote active Cd, and intensify Cd mobilization in red soil. In contrast, small-size MPs in cinnamon soil promoted the synthesis and secretion of rhizosphere amino acids and soil metabolites, thus promoting Cd absorption by maize roots. Soil microorganisms also improved Cd bioavailability via C-related functional bacteria. Overall, our study provides novel insights on the potential effects of combined MPs and Cd pollution on soil ecology and agricultural production, enhancing our understanding of rhizosphere metabolites in different soils.

Under flooding conditions, controlled-release fertiliser coated microplastics affect the growth and accumulation of cadmium in rice by increasing the fluidity of cadmium and interfering with metabolic pathways.

The combined pollution of microplastics (MPs) and Cd can affect plant growth and development and Cd accumulation, with most studies focusing on dryland soil. However, the effects of polyurethane (PU) controlled-release fertiliser coated MPs (PU MPs), which widely exist in rice systems, coupled with Cd on plant growth and Cd accumulation under flooding conditions are still unknown. Therefore, in the present study, in situ techniques were used to systematically study the effects of PU MPs and Cd coupling on the physiological and biochemical performance, metabolomics characteristics, rhizosphere bacterial community, and Cd bioavailability of rice in different soil types (red soil/cinnamon soil). The results showed that the effects of PU MPs on rice growth and Cd accumulation were concentration-dependent, especially in red soil. High PU concentration (1 %) inhibited rice root growth significantly (44 %). The addition of PU MPs inhibited photosynthetically active radiation, net photosynthesis, and transpiration rate of rice, mainly with low concentration (0.1 %) in red soil and high concentration (1 %) in cinnamon soil. PU MPs can enhance the expression of Cd resistance genes (cadC and copA) in soil, enhance the mobility of Cd, and affect the metabolic pathways of metabolites in the rhizosphere soil (red soil: fatty acid metabolism; cinnamon soil: amino acid degradation, heterobiodegradation, and nucleotide metabolism) to promote Cd absorption in rice. Especially in red soil, Cd accumulation in the root and aboveground parts of rice after the addition of high concentration PU (1 %) was 1.7 times and 1.3 times, respectively, that of the control (p < 0.05). Simultaneously, microorganisms can affect rice growth and Cd bioavailability by affecting functional bacteria related to carbon, iron, sulfur, and manganese. The results of the present study provide novel insights into the potential effects of PU MPs coupled with Cd on plants, rhizosphere bacterial communities, and Cd bioavailability.

Typical microplastics in field and facility agriculture dynamically affect available cadmium in different soil types through physicochemical dynamics of carbon, iron and microbes.

Combined pollution from microplastics (MPs) and other environmental pollutants has attracted considerable attention. Few studies have investigated the effects of polyurethane (PU) and polypropylene (PP) MPs on available Cadmium(Cd) in different soil types. Here, PU and PP additions affected available Cd and reduced its concentration in soil (P > 0.05). PU and PP reduced available Cd more strongly in clay soil than that in sandy soil. PU and PP improved the soil porous structure and voids and significantly increased the Zeta potential in clay soil (P < 0.05). Dissolved organic carbon and pH in clay soil were significantly negatively correlated with available Cd after PU and PP addition, and Fe(Ⅱ) was significantly negatively correlated with available Cd in sandy soil. PU and PP addition promoted the C-C, CO32-, and C-H functional groups and FeO, FeOOH, and Fe3O4 formation and influenced the effective Cd through adsorption and precipitation. CdCO3 formation and clay mineral adsorption, and iron oxide formation, influenced the effective Cd in clay and sandy soils, respectively. PU and PP influenced the effective state of Cd by affecting bacterial communities related to carbon and iron cycles. This study is significant for assessing the environmental risks of MPs combined with heavy metals in different soils and their mechanisms.

Ambient Pressure X-ray Photoelectron Spectroscopy Investigation of Thermally Stable Halide Perovskite Solar Cells via Post-Treatment.

Long-term thermal stability is one limiting factor that impedes the commercialization of the perovskite solar cell. Inspired by our prior results from machine learning, we discover that coating a thin layer of 4,4'-dibromotriphenylamine (DBTPA) on top of a CH3NH3PbI3 layer can improve the stability of resultant solar cells. The passivated devices kept 96% of the original power conversion efficiency for 1000 h at 85 °C in a N2 atmosphere without encapsulation. Near-ambient pressure X-ray photoelectron spectroscopy (XPS) was employed to investigate the evolution of the composition and evaluate thermal and moisture stability by in situ studies. A comparison between pristine MAPbI3 films and DBTPA-treated films shows that the DBTPA treatment suppresses the escape of iodide and methylamine up to 150 °C under 5 mbar humidity. Furthermore, we have used attenuated total reflection Fourier transform infrared and XPS to probe the interactions between DBTPA and MAPbI3 surfaces. The results prove that DBTPA coordinates with the perovskite by Lewis acid-base and cation-π interaction. Compared with the 19.9% efficiency of the pristine sample, the champion efficiency of the passivated sample reaches 20.6%. Our results reveal DBTPA as a new post-treating molecule that leads not only to the improvement of the photovoltaic efficiency but also thermal and moisture stability.