An innovative approach for inserting metal cations into layered perovskite oxides is investigated using a soft-chemistry route that enables controlled incorporation of cations such as Cu²⁺. Starting from the Ruddlesden-Popper...

Ulcerative colitis (UC) is a chronic and recurrent digestive tract disease that can lead to significant morbidity and mortality. The pathogenesis of UC is intricately associated with the presence of reactive oxygen species (ROS). Prussian blue (PB), an inorganic nanozyme with potent antioxidant properties, has been extensively applied in the treatment of various inflammatory conditions and tumors. However, despite the explicit antioxidant properties, the underlying molecular mechanism of PB nanozyme in the treatment of UC remains poorly understood. Furthermore, there is a deficiency in antioxidants that possess specific targeting capabilities towards UC lesions. The present study pioneered the fabrication of neutrophil (N)-macrophage (M) hybrid membrane-coated PB (NM-PB) nanozyme for the treatment of UC and investigated its underlying molecular mechanism. We have successfully constructed PB, N-PB, M-PB, and NM-PB nanozymes. In both the colitis cell model and UC mouse model, compared with PB, N-PB, and M-PB nanozymes, NM-PB nanozymes exhibited remarkable targeting capabilities, significantly enhancing the localization and uptake of PB nanozymes at the lesion site. NM-PB nanozymes significantly reduced levels of ROS (•OH, •OOH, and H2O2) and decreased the production of proinflammatory cytokines (TNF-α, IL-6, IL-1β). Meanwhile, these nanozymes regulated the expression of intestinal mucosal barrier-related proteins (ZO-1, E-cadherin, and Occludin) and apoptosis-related proteins (Bcl2, Bax). Furthermore, NM-PB nanozymes facilitated the polarization of proinflammatory M1-phenotype macrophage towards an anti-inflammatory M2-phenotype. The mechanistic studies demonstrated that NM-PB nanozymes mitigated the progression of UC by inhibiting the pathway of cytokine-cytokine receptor interaction. The NM-PB nanozymes provide a promising and innovative alternative for the treatment of UC, offering enhanced targeting and efficacy through their unique design and mechanism of action.

Despite previous explorations of reaction conditions (temperature, time, solvent), the construction mechanism of mesoporous titania‐bisphosphonate hybrids remains under‐researched. This study provides a further understanding of the construction mechanism of these materials by investigating the formation of key chemical bonds Ti─OAc (acetoxylation), Ti─O─Ti (TiO 2 formation), and Ti─O─P (bisphosphonate cross‐linking). It is found that the competitive reactions between Ti─O─Ti and Ti─O─P significantly influence the specific surface areas, average pore sizes, crystallite sizes, and the degree of condensation. In addition, the Ac 2 O/Ti molar ratio plays a crucial role in determining the texture and composition of the resulting hybrids. This study will guide the synthesis strategy and regulate the texture and composition of these new mesoporous nonsiliceous materials with great application potential.

Patients with inflammatory bowel disease (IBD) demonstrate varying expression levels of long non-coding RNAs (lncRNAs) in their intestinal mucosa, which can potentially impact the function of the intestinal barrier. This impact may occur through the modulation of epithelial cell apoptosis, alteration of intestinal mucosal barrier permeability, and enhancement of inflammatory responses. The objective of this study was to explore the role and underlying mechanisms of the downregulated lncRNA ANRIL in modulating intestinal barrier function in IBD. Notably, ANRIL was found to be significantly downregulated in patients diagnosed with ulcerative colitis (UC), correlating strongly with disease progression. The overexpression of ANRIL in mice treated with dextran sulfate sodium (DSS) resulted in a significant reduction in colonic damage. This was accompanied by the suppression of pro-inflammatory cytokines such as IL-6, TNF-α, and IL-1β, and an improvement in intestinal barrier function. Transcriptome sequencing following overexpression of ANRIL revealed a significant enrichment of the NF-κB signaling pathway. In both DSS-induced mouse colitis and LPS-induced FHC cell models, the upregulation of ANRIL effectively suppressed the activation of the NF-κB pathway. Furthermore, our findings demonstrated that ANRIL competes with YY1 for binding, thereby inhibiting the interaction between YY1 and p65 subunit of NF-κB. This disruption in interaction results in the suppression of transcriptional activation of NF-κB p65, leading to a reduced expression of inflammatory cytokines and the promotion of intestinal barrier function in IBD.Additionally, we identified a negative feedback loop involving ANRIL and p65, wherein p65 binds to the ANRIL promoter, promoting ANRIL expression. In summary, the ANRIL/p65 negative feedback loop represents a potential therapeutic target for protecting intestinal barrier function in IBD.

Combining the properties of organic and inorganic components with high surface areas and large pore volumes opens up countless possibilities for designing materials tailored to a wide range of advanced applications. As the majority of mesoporous hybrid materials are siliceous, the development of cost-effective synthetic approaches to produce water-stable hybrids with controlled porosity and functionality remains essential. Herein, we describe an original strategy for the synthesis of bridged mesoporous titania–bisphosphonate hybrids based on a one-step, template-free, non-hydrolytic sol–gel process. The reaction between Ti(OiPr)4 and several flexible or rigid bisphosphonate esters, in the presence of acetic anhydride (Ac2O) leads to the formation of TiO2 anatase nanorods interconnected by fully condensed bisphosphonate groups. The general method that we depict is quantitative and low cost. All materials are mesoporous with very high specific surface areas (up to 520 m2·g⁻1) and pore volumes (up to 0.93 cm3·g⁻1).

Background: Ulcerative colitis (UC) is a chronic, recurrent, non-specific inflammatory disease, and the pathogenesis of the disease remains unclear. Ferroptosis is a form of programmed cell death characterized by the accumulation of iron-dependent lipid peroxides, which are simultaneously closely related to reactive oxygen species (ROS). Although seliciclib is highly effective against immune inflammation, its mechanism on colitis is unclear. This study demonstrated that seliciclib administration partially inhibited ferroptosis, alleviating symptoms and inflammation in experimental colitis. Methods: The mouse UC model was induced by 3.0 % dextran sodium sulfate (DSS) for 7 days and treated with seliciclib (10 mg/kg) for 5 days. In the in vitro model, LPS (100 mu g/mL) was used for induction and seliciclib (10 mu M) was applied for 2 h. Meanwhile, appropriate histopathology, inflammatory response, oxidative stress, and ferroptosis regulators were measured. Results: This study primarily investigated the role of seliciclib in regulating ferroptosis in UC. Bioinformatics analysis indicated that Dual oxidase 2 (DUOX2) may serve a role involved in the ferroptosis of UC. The experimental findings demonstrated that seliciclib alleviates symptoms and inflammation in DSS-induced UC mice and partially mitigates the occurrence of ferroptosis both in vivo and in vitro, possibly through the modulation of DUOX2. Conclusions: Ferroptosis is strongly associated with the development of colitis, and seliciclib plays an essential role in ferroptosis and inflammation in UC. The suppression of ferroptosis in the intestinal epithelium could be a therapeutic approach for UC.

Oxalic acid (C2) is a significant tracer of secondary organic aerosols (SOA), yet its precursors, evolutionary processes, and formation mechanisms are not fully understood. This knowledge gap leads to uncertainties in evaluating the climate effect and global budget of SOA. Here we compared the size distribution, mixing fraction, and evolutionary mechanism of C2-containing particles between summer and winter. In summer, the number of C2 particles and their homologs decreased compared to winter. However, the proportion of C2 relative to the total number of determined particles increased, indicating that the summertime particles are more aged. Higher relative aerosol acidity (Rra) and lower in-situ pH (pHis) in summer suggest that particles are more acidic during this season. Correlation analysis and temporal variation characteristics suggest that from 9: 00 to 15: 00 in summer, C2 particles mostly originate from the photochemical decomposition of larger dicarboxylic aids, driven by O3 concentration. Conversely, from 16: 00 to 20: 00, C2 particles are predominantly formed through aqueous-phase oxidation, influenced by higher relative humidity (RH), aerosol liquid water content (ALWC), and acidity. Additionally, heavy metal particles were the predominant type of C2 particles, and C2 particles exhibited an opposite diurnal variation to Fe in summer, suggesting that the photolysis of iron oxalate complexes is an important sink of C2 particles during this period. In winter, biomass burning (BB) particles were the most abundant, and a robust correlation between levoglucosan and C2 particles indicated a substantial influence of BB on C2 particles. The aqueous generation of C2 particles from α-dicarbonyls driven by acidity was most effective when RH varied from 40% to 60% in the wintertime state of particles. These findings highlight the hourly and seasonal variations in the sources and evolutionary processes of SOA. Such variations must be considered in developing control measures and simulating the climate effect of SOA.

Organic aerosols (OAs) are key components of atmospheric PM 2.5, which impose an important influence on citizens' health and atmospheric chemistry. However, the vertical distribution and evolutionary mechanisms of OAs have remained unclear, posing challenges for accurate model simulations. To compare the difference in molecular distribution and sources at different altitudes and explore the impact of vertical transport of mountain- valley breezes on OAs in mountainous regions, PM 2.5 samples were simultaneously collected at both the summit (SM: 1840 m a.s.l) and the foot Mt. Huang (FM: 480 m a.s.l.) in winter. All the 128 detected organic species presented higher concentrations at FM (237 +/- 118 ng m(-3)) than at SM (89.3 +/- 40.9 ng m(-3)), indicating that the influence of anthropogenic emissions on OAs became more significant as elevation decreased. Levoglucosan was the dominant single organic species and displayed robust correlations with most organic components at both sites, suggesting the notable effect of biomass burning on OAs in the alpine atmosphere. Molecular composition, characteristic ratios, and positive matrix factorization analysis suggested that OAs at SM were more aged and mostly derived from secondary oxidation and biomass burning from long-range transport. However, anthropogenic sources (e.g., biomass burning and fossil fuel combustion) contributed more to OAs at FM. Potential source contribution function results revealed that the northeastern part of Jiangxi Province and the nearby regions of the observation point are the potential source regions for OAs at FM, while long-range transport from northwestern Anhui Province and northern Jiangxi Province played a key role in OAs at SM. This study proved that OAs at FM could influence the mountaintop aerosols through the vertical transport of valley breeze in the day at Mt. Huang. These findings enhance our understanding of the vertical distribution of OAs and provide a scientific foundation for cross-regional atmospheric pollution control.

Shrink fitting of forging mold (SFFM) is an effective method for improving mold strength, extending the mold’s service life and reducing the manufacturing cost of forging mold. However, due to the asymmetric geometry and complex stress distribution, the precise design of SFFM for the precision forging of noncircular bevel gears is very difficult. In this paper, a new precise design method of SFFM for the precision forging of noncircular bevel gears is proposed, which mainly includes the following five parts. First, a new design method for the mold parting surface—the curved surface parting method—is proposed to design the forging mold of noncircular spur bevel gears. Then, new dimension design methods for the gear mold and shrink rings based on the uniform shrinkage force are proposed. Third, a new design method for the inhomogeneous interference value between shrink rings and the gear mold is developed to provide a precise, uniform shrinkage force. After that, a strength correction method for the shrink-fitted gear mold is proposed to ensure the gear mold and shrink rings have sufficient strength both in the assembly process of the shrink-fitted gear mold and precision in the forging process of noncircular spur bevel gears. Ultimately, finite element simulations and verification experiments are performed to verify the proposed precise design method of SFFM for the precision forging of noncircular bevel gears. The precise design method of SFFM proposed in this paper is not only applicable to the precise design of the high-strength gear mold for noncircular bevel gears, but can also provide a valid reference for the precise design of the high-strength mold for other complicated asymmetric parts.

A highly diastereoselective Pd(0)-catalyzed Mizoroki-Heck reaction of gem-difluoroalkenes is described. Unlike previously reported C-F bond functionalization with organometallic reagents, this reaction takes place between two different alkenes to achieve a formal C-F and C-H bond cross-coupling via a distinct pathway. Monofluorinated 1,3-diene products can be synthesized with control of the geometry of each alkene and good functional group tolerability.

Under typical copper-catalyzed hydroboration conditions, β-(trifluoromethyl)styrenes demonstrate unusal reactivities by forming difluoromethylated alkenes via a net protodefluorination process. This is also distinct from trifluoromethyl alkenes with alkyl substituents where defluoroborylation products predominate.

Background: Non-small cell lung cancer (NSCLC) is a leading cause of cancer death. Branched-chain amino acid (BCAA) homeostasis is important for normal physiological metabolism. Branched-chain keto acid dehydrogenase kinase (BCKDK) is a rate-limiting enzyme involved in BCAA degradation. BCAA metabolism has been highlighted in human cancers. The aberrant activation of mTORC1 has been implicated in tumor progression. Rab1A is a small GTPase, an activator of mTORC1, and an oncogene. This study aimed to reveal the specific role of BCKDK-BCAA-Rab1A-mTORC1 signaling in NSCLC. Methods: We analyzed a cohort of 79 patients with NSCLC and 79 healthy controls. Plasma BCAA assays, immunohistochemistry, and network and pathway analyses were performed. The stable cell lines BCKDK-KD, BCKDK-OV A549, and H1299 were constructed. BCKDK, Rab1A, p-S6 and S6 were detected using western blotting to explore their molecular mechanisms of action in NSCLC. The effects of BCAA and BCKDK on the apoptosis and proliferation of H1299 cells were detected by cell function assays.Results: We demonstrated that NSCLC was primarily involved in BCAA degradation. Therefore, combining BCAA, CEA, and Cyfra21-1 is clinically useful for treating NSCLC. We observed a significant increase in BCAA levels, downregulation of BCKDHA expression, and upregulation of BCKDK expression in NSCLC cells. BCKDK promotes proliferation and inhibits apoptosis in NSCLC cells, and we observed that BCKDK affected Rab1A and p-S6 in A549 and H1299 cells via BCAA modulation. Leucine affected Rab1A and p-S6 in A549 and H1299 cells and affected the apoptosis rate of H1299 cells.In conclusion, BCKDK enhances Rab1A-mTORC1 signaling and promotes tumor proliferation by suppressing BCAA catabolism in NSCLC, suggesting a new biomarker for the early diagnosis and identification of metabolism-based targeted approaches for patients with NSCLC.

Secondary organic aerosol (SOA) exerts a considerable influence on atmospheric chemistry. However, little information about the vertical distribution of SOA in the alpine setting is available, which limited the simulation of SOA using chemical transport models. Here, a total of 15 biogenic and anthropogenic SOA tracers were measured in PM2.5 aerosols at both the summit (1840 m a.s.l.) and foot (480 m a.s.l.) of Mt. Huang during the winter of 2020 to explore their vertical distribution and formation mechanism. Most of the determined chemical species (e.g., BSOA and ASOA tracers, carbonaceous components, major inorganic ions) and gaseous pollutants at the foot of Mt. Huang were 1.7-3.2 times higher concentrations than those at the summit, suggesting the relatively more significant effect of anthropogenic emissions at the ground level. The ISORROPIA-II model showed that aerosol acidity increases as altitude decreases. Air mass trajectories, potential source contribution function (PSCF), and correlation analysis of BSOA tracers with temperature revealed that SOA at the foot of Mt. Huang was mostly derived from the local oxidation of volatile organic compounds (VOCs), while SOA at the summit was mainly influenced by long-distance transport. The robust correlations of BSOA tracers with anthropogenic pollutants (e.g., NH3, NO2, and SO2) (r = 0.54-0.91, p < 0.05) indicated that anthropogenic emissions could promote BSOA productions in the mountainous background atmosphere. Moreover, most of SOA tracers (r = 0.63-0.96, p < 0.01) and carbonaceous species (r = 0.58-0.81, p < 0.01) were correlated well with levoglucosan in all samples, suggesting that biomass burning played an important role in the mountain troposphere. This work demonstrated that daytime SOA at the summit of Mt. Huang was significantly influenced by the valley breeze in winter. Our results provide new insights into the vertical distributions and provenance of SOA in the free troposphere over East China.

Plasmonic nanostructures have been demonstrated for their application in thin film solar cells to enhance absorption. Of particular concern is the novel design, enabling the broadband absorption enhancement. Here, we proposed and implemented a periodic corrugated Au nanomesh for broadband light absorption enhancement. By combining plasmon treatment of pre-stretched substrate and nanosphere lithography, the Au nanomesh on the nanocorrugation with different period has been realized. Compared to the planar nanomesh, the periodic corrugated nanomesh exhibits observable absorption enhancement at broad wavelength range, especially from 700[Formula: see text]nm to 1000[Formula: see text]nm, which is of significance in bring solar energy up to more utilization due to poor absorption of thin film solar cells at the near-infrared band. The enhancement attributes to the spatially geometry deformation of nanomesh supported more plasmonic resonance at the different adjacent frequency. Also, the absorption enhancement is relative to the period of corrugation, which caused by the variation of geometry deformation amplitude of nanomesh. This periodic corrugated metallic nanomesh provides an alternative nanostructured electrode to broadband absorption enhancement for thin film solar cell application.

The molecular characteristics and formation mechanism of biogenic secondary organic aerosols (BSOAs) in the forested atmosphere are poorly known. Here, we report the temporal variations in and formation processes of BSOA tracers derived from isoprene, monoterpenes, and β caryophyllene in PM2.5 samples collected at the foot of Mt. Huang (483 m a. s. l) in East China during the summer of 2019 with a 3 h time resolution. The concentrations of nearly all of the detected species, including organic carbon (OC), elemental carbon (EC), levoglucosan, and SIA (sum of SO42−, NO3−, and NH4+), were higher at night (19:00–7:00 of the next day) than in the daytime (7:00–19:00). In addition, air pollutants that accumulated by the dynamic transport of the mountain breeze at night were also a crucial reason for the higher BSOA tracers. Most of the BSOA tracers exhibited higher concentrations at night than in the daytime and peaked at 1:00 to 4:00 or 4:00 to 7:00. Those BSOA tracers presented strong correlations with O3 in the daytime rather than at night, indicating that BSOAs in the daytime were primarily derived from the photo-oxidation of BVOCs with O3. The close correlations of BSOA tracers with SO42− and particle acidity (pHis) suggest that BSOAs were primarily derived from the acid-catalyzed aqueous-phase oxidation. Considering the higher relative humidity and LWC concentration at night, the promoted aqueous oxidation was the essential reason for the higher concentrations of BSOA tracers at night. Moreover, levoglucosan exhibited a robust correlation with BSOA tracers, especially β-caryophyllinic acid, suggesting that biomass burning from long-distance transport exerted a significant impact on BSOA formation. Based on a tracer-based method, the estimated concentrations of secondary organic carbon (SOC) derived from isoprene, monoterpenes, and β caryophyllene at night (0.90 ± 0.57 µgC m−3) were higher than those (0.53 ± 0.34 µgC m−3) in the daytime, accounting for 14.5 ± 8.5% and 12.2 ± 5.0% of OC, respectively. Our results reveal that the BSOA formation at the foot of Mt. Huang was promoted by the mountain-valley breezes and anthropogenic pollutants from long-range transport.

Different titanium phosphonates were in situ synthesized within a polymer matrix via non-hydrolytic sol-gel reactions to elaborate nanocomposites with 10 wt% filler content. Titanium tetraacetate was used as titanium dioxide precursor. Three diethyl phosphonates with different organic groups were selected depending on the polymer medium, polypropylene or polystyrene respectively. Polymer/titanium phosphonate nanocomposites obtained were characterized by TGA, FTIR and 31P solid-state NMR spectroscopies, XRD and electron microscopy. For the polypropylene-based composite, the titanium phosphonate fillers synthesized from diethyl octylphosphonate (DEOP) exhibited an average size of 900 nm and appeared well-dispersed. XRD experiments demonstrated the absence of signal corresponding to crystalline layered titanium phosphonate. With polystyrene, two diethyl phosphonate molecules containing aromatic groups were used to obtain composites. The diethyl benzylphosphonate (DEBP) led to the formation of agglomerates of about 490 nm whereas diethyl phenylphosphonate (DEPP) led to the formation of bigger fillers. However, both systems led to the appearance of fillers with a platelet-like morphology. These results confirmed the significant impact of the solvent (here viscous polymer medium) on the growth and morphology of the created objects.

Ulcerative colitis, an inflammatory bowel disease, manifests with symptoms such as abdominal pain, diarrhea, and mucopurulent feces. The long non-coding RNA (lncRNA) ANRIL exhibits significantly reduced expression in UC, yet its specific mechanism is unknown. This study revealed that ANRIL is involved in the progression of UC by inhibiting IL-6 and TNF-α via miR-191-5P/SATB1 axis. We found that in patients with UC, interleukin-6 (IL-6) and tumor necrosis factor-α (TNF-α) were significantly overexpressed in inflamed colon sites, whereas ANRIL was significantly under-expressed and associated with disease severity. The downregulation of ANRIL resulted in the increased expression of IL-6 and TNF-α in LPS-treated FHCs. ANRIL directly targeted miR-191-5p, thereby inhibiting its expression and augmenting SATB1 expression. Moreover, overexpression of miR-191-5p abolished ANRIL-mediated inhibition of IL-6 and TNF-α production. Dual luciferase reporter assays revealed the specific binding of miR-191-5p to ANRIL and SATB1. Furthermore, the downregulation of ANRIL promoted DSS-induced colitis in mice. Together, we provide evidence that ANRIL plays a critical role in regulating IL-6 and TNF-α expression in UC by modulating the miR-191-5p/SATB1 axis. Our study provides novel insights into progression and molecular therapeutic strategies in UC.

We herein describe selective C-F bond functionalizations of tetrasubstituted gem-difluoroalkenes and trisubstituted monofluoroalkenes using Grignard reagents without the transition metal catalyst. β,β-Difluoroacrylates react with Grignard reagents under mild conditions to afford tetrasubstituted (E)-β-monofluoroacrylates. Experimental and computational studies revealed that the selectivity stems from the intrinsic reactivity difference between the (E)- and (Z)-isomers toward excess Grignard reagent, which leads to the resolution of the two products.

Herein, we reported the synthesis of TiO2 through different non-hydrolytic sol-gel (NHSG) routes in viscous polymer media. For the first time, the influence of the polymer nature (Polystyrene (PS) or Polypropylene (PP)) on the morphology of synthesized inorganic domains was investigated. The non-hydrolytic sol-gel reactions between titanium isopropoxide Ti(OiPr)4 and acetic anhydride in molten polypropylene lead to the formation of microfillers with a mean diameter of about 1 μm, while the same synthesis carried out in viscous polystyrene lead to the formation of nanofillers with diameter lower than 10 nm forming aggregates of approximately 200 nm. We have also investigated the influence of the oxygen donor nature on the morphology of synthesized fillers using aromatic oxygen donors in a polystyrene matrix. The use of benzoic anhydride or acetophenone as oxygen donors with Ti(OiPr)4 in viscous polystyrene lead to respectively platelet-like morphology or aggregated nanofillers. We demonstrated that the affinity between polymer, reactants, and/or by-products had an influence on the morphology and the size of in situ synthesized TiO2 fillers. These results evidenced for the first time the possibility to control and to tune the morphology of in situ grown inorganic objects through the NHSG process by the appropriate choice of solvent, here a viscous polymer medium, and reactants.

An original way to synthesise polypropylene/titanium dioxide (PP/TiO2) composites combining non-hydrolytic sol–gel chemistry and reactive extrusion was reported. The non-hydrolytic sol–gel reaction between titanium alkoxide as a titanium dioxide precursor and an acid anhydride as an oxygen donor at 240 °C was first evaluated and optimised in an alkane liquid medium. TiO2 was present essentially in crystalline anatase form when synthesised in squalane with a domain size around 10 nm. Based on these encouraging results, the synthesis was adapted to reactive extrusion that means at high temperature in molten viscous polypropylene and for short reaction times (few minutes maximum). The proof of concept was evidenced through the formation of amorphous TiO2-based inorganic domains of size around 1 µm within the polymer matrix from the reaction between titanium isopropoxide and acetic anhydride. A condensation degree of 79% was obtained. To optimise the polymer/filler interface, titanium dioxide precursors and oxygen donors with different alkyl chain lengths were evaluated. Hexanoic anhydride as substituent of acetic anhydride and titanium tetrakis 2-ethylhexyloxide as substituent of titanium isopropoxide were used. The oxygen donor contribution appeared to be dominant for the particle dispersion state. The polypropylene (PP)/TiO2 composite synthesised from the reaction between titanium isopropoxide and hexanoic anhydride showed the narrowest TiO2 particle diameter distribution with a mean particle size around 700 nm.