Noncrystalline Zeolitic Imidazolate Frameworks Tethered with Ionic Liquids as Catalysts for CO2 Conversion into Cyclic Carbonates.

Noncrystalline zeolitic imidazolate frameworks (ZIFs) tethered with ionic liquids (ILs) were successfully employed as catalysts for mild CO2 conversion into cyclic carbonates for the first time. Notably, noncrystalline ZIFs exhibit outstanding catalytic performance in terms of activity, stability, and substrate suitability. Z3 was obtained through the simultaneous incorporation of a boronic acid group and ILs into its ZIF framework and exhibited a superior catalytic activity. A reaction mechanism for the propylene oxide-CO2 cycloaddition has been proposed, which integrates experimental findings with density functional theory calculations. The results indicate that zinc, ILs, and boronic acid play crucial roles in achieving high activity. Zinc and ILs are identified as key contributors to epoxide activation and ring opening, while boronic acid plays a crucial role in stabilizing the turnover frequency-determining transition states. The simplicity of this ZIF synthesis approach, combined with the high activity, stability, and versatility of the products, facilitates practical and efficient conversion of CO2 and epoxides into cyclic carbonates.

Apoptosis and pyroptosis in the nasal mucosa of Syrian hamster during SARS-CoV-2 infection and reinfection.

In SARS-CoV-2 infection, it has been observed that viral replication lasts longer in the nasal mucosa than in the lungs, despite the presence of a high viral load at both sites. In hamsters, we found that the nasal mucosa exhibited a mild inflammatory response and minimal pathological injuries, whereas the lungs displayed a significant inflammatory response and severe injuries. The underlying cellular events may be induced by viral infection in three types of cell death: apoptosis, pyroptosis, and necroptosis. Our findings indicate that apoptosis was consistently activated during infection in the nasal mucosa, and the levels of apoptosis were consistent with the viral load. On the other hand, pyroptosis and a few instances of necroptosis were observed only on 7 dpi in the nasal mucosa. In the lungs, however, both pyroptosis and apoptosis were prominently activated on 3 dpi, with lower levels of apoptosis compared to the nasal mucosa. Interestingly, in reinfection, obvious viral load and apoptosis in the nasal mucosa were detected on 3 dpi, while no other forms of cell death were detected. We noted that the inflammatory reactions and pathological injuries in the nasal mucosa were milder, indicating that apoptosis may play a role in promoting lower inflammatory reactions and milder pathological injuries and contribute to the generation of long-term viral replication in the nasal mucosa. Our study provides valuable insights into the differences in cellular mechanisms during SARS-CoV-2 infection and highlights the potential significance of apoptosis regulation in the respiratory mucosa for controlling viral replication.

Exfoliation of Metal-Organic Frameworks to Give 2D MOF Nanosheets for the Electrocatalytic Oxygen Evolution Reaction.

The structure and properties of materials are determined by a diverse range of chemical bond formation and breaking mechanisms, which greatly motivates the development of selectively controlling the chemical bonds in order to achieve materials with specific characteristics. Here, an orientational intervening bond-breaking strategy is demonstrated for synthesizing ultrathin metal-organic framework (MOF) nanosheets through balancing the process of thermal decomposition and liquid nitrogen exfoliation. In such approach, proper thermal treatment can weaken the interlayer bond while maintaining the stability of the intralayer bond in the layered MOFs. And the following liquid nitrogen treatment results in significant deformation and stress in the layered MOFs' structure due to the instant temperature drop and drastic expansion of liquid N2, leading to the curling, detachment, and separation of the MOF layers. The produced MOF nanosheets with five cycles of treatment are primarily composed of nanosheets that are less than 10 nm in thickness. The MOF nanosheets exhibit enhanced catalytic performance in oxygen evolution reactions owing to the ultrathin thickness without capping agents which provide improved charge transfer efficiency and dense exposed active sites. This strategy underscores the significance of orientational intervention in chemical bonds to engineer innovative materials.

Dexamethasone Induced Osteocyte Apoptosis in Steroid-Induced Femoral Head Osteonecrosis through ROS-Mediated Oxidative Stress.

OBJECTIVE: Glucocorticoid (GC) overuse is strongly associated with steroid-induced osteonecrosis of the femoral head (SINFH). However, the underlying mechanism of SINFH remains unclear. This study aims to investigate the effect of dexamethasone (Dex)-induced oxidative stress on osteocyte apoptosis and the underlying mechanisms. METHODS: Ten patients with SINFH and 10 patients with developmental dysplasia of the hips (DDH) were enrolled in our study. Sixty rats were randomly assigned to the Control, Dex, Dex + N-Acetyl-L-cysteine (NAC), Dex + Dibenziodolium chloride (DPI), NAC, and DPI groups. Magnetic resonance imaging (MRI) was used to examine edema in the femoral head of rats. Histopathological staining was performed to assess osteonecrosis. Immunofluorescence staining with TUNEL and 8-OHdG was conducted to evaluate osteocyte apoptosis and oxidative damage. Immunohistochemical staining was carried out to detect the expression of NOX1, NOX2, and NOX4. Viability and apoptosis of MLO-Y4 cells were measured using the CCK-8 assay and TUNEL staining. 8-OHdG staining was conducted to detect oxidative stress. 2',7'-Dichlorodihydrofluorescein diacetate (DCFH-DA) staining was performed to measure reactive oxygen species (ROS). The expression of NOX1, NOX2, and NOX4 in MLO-Y4 cells was analyzed by Western blotting. Multiple comparisons were performed using one-way analysis of variance (ANOVA). RESULTS: In patients and the rat model, hematoxylin-eosin (HE) staining revealed a significantly higher rate of empty lacunae in the SINFH group than in the DDH group. Immunofluorescence staining indicated a significant increase in TUNEL-positive cells and 8-OHdG-positive cells in the SINFH group compared to the DDH group. Immunohistochemical staining demonstrated a significant increase in the expression of NOX1, NOX2, and NOX4 proteins in SINFH patients compared to DDH patients. Moreover, immunohistochemical staining showed a significant increase in the proportion of NOX2-positive cells compared to the Control group in the femoral head of rats. In vitro, Dex significantly inhibited the viability of osteocyte cells and induced apoptosis. After Dex treatment, the intracellular ROS level increased. However, Dex treatment did not alter the expression of NOX proteins in vitro. Additionally, NAC and DPI inhibited the generation of intracellular ROS and partially alleviated osteocyte apoptosis in vivo and in vitro. CONCLUSION: This study demonstrates that GC promotes apoptosis of osteocyte cells through ROS-induced oxidative stress. Furthermore, we found that the increased expression of NOXs induced by GC serves as an important source of ROS generation.

The Abundant Distribution and Duplication of SARS-CoV-2 in the Cerebrum and Lungs Promote a High Mortality Rate in Transgenic hACE2-C57 Mice.

Patients with COVID-19 have been reported to experience neurological complications, although the main cause of death in these patients was determined to be lung damage. Notably, SARS-CoV-2-induced pathological injuries in brains with a viral presence were also found in all fatal animal cases. Thus, an appropriate animal model that mimics severe infections in the lungs and brain needs to be developed. In this paper, we compared SARS-CoV-2 infection dynamics and pathological injuries between C57BL/6Smoc-Ace2em3(hACE2-flag-Wpre-pA)Smoc transgenic hACE2-C57 mice and Syrian hamsters. Importantly, the greatest viral distribution in mice occurred in the cerebral cortex neuron area, where pathological injuries and cell death were observed. In contrast, in hamsters, viral replication and distribution occurred mainly in the lungs but not in the cerebrum, although obvious ACE2 expression was validated in the cerebrum. Consistent with the spread of the virus, significant increases in IL-1ß and IFN-γ were observed in the lungs of both animals. However, in hACE2-C57 mice, the cerebrum showed noticeable increases in IL-1ß but only mild increases in IFN-γ. Notably, our findings revealed that both the cerebrum and the lungs were prominent infection sites in hACE2 mice infected with SARS-CoV-2 with obvious pathological damage. Furthermore, hamsters exhibited severe interstitial pneumonia from 3 dpi to 5 dpi, followed by gradual recovery. Conversely, all the hACE2-C57 mice experienced severe pathological injuries in the cerebrum and lungs, leading to mortality before 5 dpi. According to these results, transgenic hACE2-C57 mice may be valuable for studying SARS-CoV-2 pathogenesis and clearance in the cerebrum. Additionally, a hamster model could serve as a crucial resource for exploring the mechanisms of recovery from infection at different dosage levels.

Ferroelectric-Optoelectronic Hybrid System for Photodetection.

Photodetectors (PDs), as functional devices based on photon-to-electron conversion, are an indispensable component for the next-generation Internet of Things system. The research of advanced and efficient PDs that meet the diverse demands is becoming a major task. Ferroelectric materials can develop a unique spontaneous polarization due to the symmetry-breaking of the unit cell, which is switchable under an external electric field. Ferroelectric polarization field has the intrinsic characteristics of non-volatilization and rewritability. Introducing ferroelectrics to effectively manipulate the band bending and carrier transport can be non-destructive and controllable in the ferroelectric-optoelectronic hybrid systems. Hence, ferroelectric integration offers a promising strategy for high-performance photoelectric detection. This paper reviews the fundamentals of optoelectronic and ferroelectric materials, and their interactions in hybrid photodetection systems. The first section introduces the characteristics and applications of typical optoelectronic and ferroelectric materials. Then, the interplay mechanisms, modulation effects, and typical device structures of ferroelectric-optoelectronic hybrid systems are discussed. Finally, in summary and perspective section, the progress of ferroelectrics integrated PDs is summed up and the challenges of ferroelectrics in the field of optoelectronics are considered.

Synthesis of Pd/Carbon Hollow Spheres by the Microwave Discharge Method for Catalytic Debenzylation.

Pd/C catalysts have been widely applied in the debenzylation process due to their excellent ability of hydrogenolysis. However, they have been suffering from the problems of agglomeration and loss of active components, which lead to decreased and unstable activity. Thus, it is still a challenge to achieve Pd/C catalysts with high activity and stability. Herein, we propose a strategy for preparing Pd/C catalysts on porous carbon hollow spheres by a microwave discharge method. Due to the high-temperature property and reducibility of microwave discharge, Pd precursors can be rapidly reduced, resulting in well-dispersed Pd nanoparticles with a small size on the carbon carrier. Besides, the matched mesopores in the carbon hollow spheres can anchor Pd nanoparticles and effectively reduce the agglomeration and loss of Pd nanoparticles during the catalytic reaction. As a result, the as-prepared Pd/mesoporous carbon hollow spheres exhibit high and stable activity in the debenzylation reaction.

Palladium-Catalyzed Regioselective C4-H Acyloxylation of Indoles with Carboxylic Acids via a Transient Directing Groups Strategy.

The development of an efficient method for the synthesis of C4 oxy-substituted indoles is an appealing yet challenging task. Herein, we report a general palladium-catalyzed TDG approach for the direct C4-H acyloxylation of indoles. The protocol features atom and step economy, excellent regioselectivity, and good tolerance of functional groups. Moreover, the reaction can accommodate a range of carboxylic acids including benzoic acids, phenylacetic acids, and aliphatic acids.

Causal association of epigenetic aging and osteoporosis: a bidirectional Mendelian randomization study.

BACKGROUND: The relationship between aging and osteoporosis is well established. However, the relationship between the body's physiological age, i.e. epigenetic age, and osteoporosis is not known. Our goal is to analyze the bidirectional causal relationship between epigenetic clocks and osteoporosis using a bidirectional Mendelian randomization study. METHODS: We used SNPs closely associated with GrimAge, Hannum, PhenoAge, and HorvathAge in epigenetic age and SNPs closely associated with femoral neck bone mineral density, lumbar spine bone mineral density, and forearm bone mineral density as instrumental variables, respectively, using the inverse variance weighting method and several other MR methods to assess the bidirectional causal relationship between epigenetic age and osteoporosis. RESULT: There was no evidence of a clear causal relationship of epigenetic age (GrimAge, Hannum, PhenoAge, and HorvathAge) on femoral neck bone mineral density, lumbar spine bone mineral density, and forearm bone mineral density. In reverse Mendelian randomization analysis showed a significant causal effect of lumbar spine bone mineral density on GrimAge: odds ratio (OR) = 0.692, 95% confidence interval (CI) = (0.538-0.890), p = 0.004. The results suggest that a decrease in lumbar spine bone mineral density promotes an acceleration of GrimAge. CONCLUSION: There was no significant bidirectional causal relationship between epigenetic age and osteoporosis A decrease in lumbar spine bone density may lead to an acceleration of the epigenetic clock "GrimAge". Our study provides partial evidence for a bidirectional causal effect between epigenetic age and Osteoporosis.

Directing group assisted para-selective C-H alkynylation of unbiased arenes enabled by rhodium catalysis.

Regioselective C-H alkynylation of arenes via C-H activation is challenging yet a highly desirable transformation. In this regard, directing group assisted C(sp2)-H alkynylation of arenes offers a unique opportunity to ensure precise regioselectivity. While the existing methods are mainly centered around ortho-C-H alkynylation and a few for meta-C-H alkynylation, the DG-assisted para-selective C-H alkynylation is yet to be reported. Herein we disclose the first report on Rh-catalyzed para-C-H alkynylation of sterically and electronically unbiased arenes. The para-selectivity is achieved with the assistance of a cyano-based directing template and the selectivity remained unaltered irrespective of the steric and electronic influence of the substituents. The post-synthetic modification of synthesized para-alkynylated arenes is also demonstrated. The mechanistic intricacies of the developed protocol are elucidated through experimental and computational studies.

Polo-like kinase 1 suppresses lung adenocarcinoma immunity through necroptosis.

Polo-like kinase 1 (PLK1) plays a crucial role in cell mitosis and has been associated with necroptosis. However, the role of PLK1 and necroptosis in lung adenocarcinoma (LA) remains unclear. In this study, we analyzed The Cancer Genome Atlas (TCGA) and Genotype-Tissue Expression databases to evaluate the prognostic value and mechanistic role of PLK1 in LA. PLK1 was found to be highly expressed in LA and was positively associated with advanced disease staging and poor survival outcomes. Functional enrichment analysis showed that PLK1 was involved in cell mitosis, neurotransmitter transmission, and drug metabolism. Further analysis using single-sample gene set enrichment analysis and ESTIMATE algorithm revealed a correlation between PLK1 expression and immune infiltration in LA. Silencing of PLK1 using miRNA transfection in LA cells reduced cell proliferation and increased apoptosis, as well as upregulating the expression of necroptosis-related proteins, such as RIPK1, RIPK3, and MLKL. Additionally, nude mouse transplantation tumor experiments demonstrated that silencing PLK1 reduced the growth capacity of LA cells. These findings suggest that PLK1 plays a critical role in LA progression by regulating necroptosis and immune infiltration, and may serve as a potential therapeutic target for immunotherapy. Furthermore, PLK1 expression can be used as a prognostic biomarker for LA patients.

Opportunities and Challenges of Metal-Organic Framework Micro/Nano Reactors for Cascade Reactions.

Building bridges among different types of catalysts to construct cascades is a highly worthwhile pursuit, such as chemo-, bio-, and chemo-bio cascade reactions. Cascade reactions can improve the reaction efficiency and selectivity while reducing steps of separation and purification, thereby promoting the development of "green chemistry". However, compatibility issues in cascade reactions pose significant constraints on the development of this field, particularly concerning the compatibility of diverse catalyst types, reaction conditions, and reaction rates. Metal-organic framework micro/nano reactors (MOF-MNRs) are porous crystalline materials formed by the self-assembly coordination of metal sites and organic ligands, possessing a periodic network structure. Due to the uniform pore size with the capability of controlling selective transfer of substances as well as protecting active substances and the organic-inorganic parts providing reactive microenvironment, MOF-MNRs have attracted significant attention in cascade reactions in recent years. In this Perspective, we first discuss how to address compatibility issues in cascade reactions using MOF-MNRs, including structural design and synthetic strategies. Then we summarize the research progress on MOF-MNRs in various cascade reactions. Finally, we analyze the challenges facing MOF-MNRs and potential breakthrough directions and opportunities for the future.

Water-assisted hydrogen spillover in Pt nanoparticle-based metal-organic framework composites.

Hydrogen spillover is the migration of activated hydrogen atoms from a metal particle onto the surface of catalyst support, which has made significant progress in heterogeneous catalysis. The phenomenon has been well researched on oxide supports, yet its occurrence, detection method and mechanism on non-oxide supports such as metal-organic frameworks (MOFs) remain controversial. Herein, we develop a facile strategy for efficiency enhancement of hydrogen spillover on various MOFs with the aid of water molecules. By encapsulating platinum (Pt) nanoparticles in MOF-801 for activating hydrogen and hydrogenation of C=C in the MOF ligand as activated hydrogen detector, a research platform is built with Pt@MOF-801 to measure the hydrogenation region for quantifying the efficiency and spatial extent of hydrogen spillover. A water-assisted hydrogen spillover path is found with lower migration energy barrier than the traditional spillover path via ligand. The synergy of the two paths explains a significant boost of hydrogen spillover in MOF-801 from imperceptible existence to spanning at least 100-nm-diameter region. Moreover, such strategy shows universality in different MOF and covalent organic framework materials for efficiency promotion of hydrogen spillover and improvement of catalytic activity and antitoxicity, opening up new horizons for catalyst design in porous crystalline materials.

Apocynin exerts cytoprotective effects on dexamethasone-induced osteoblasts by inhibiting oxidative stress through the Nrf2 signalling pathway.

Steroid-induced femoral head necrosis (SIFHN) is a serious clinical complication that is caused by prolonged or excessive use of glucocorticoids (GCs). Osteoblast apoptosis and osteogenic differentiation dysfunction caused by GC-induced oxidative stress and mitochondrial impairment are strongly implicated in SIFHN. Apocynin (APO) is a kind of acetophenone extracted from an herb. In recent years, APO has received much attention for its antiapoptotic and antioxidant properties. This study aimed to investigate whether APO could protect against SIFHN and explore the mechanism. In our study, low-dose APO had no toxic effects on osteoblasts and restored dexamethasone (Dex)-treated osteoblasts by improving survival, inhibiting OS and restoring mitochondrial dysfunction. Mechanistically, APO alleviated Dex-induced osteoblast injury by activating the Nrf2 pathway, and the use of ML385 to block Nrf2 significantly eliminated the protective effect of APO. In addition, APO could reduce the formation of empty lacunae, restore bone mass and promote the expression of Nrf2 in SIFHN rats. In conclusion, APO protects osteoblasts from Dex-induced oxidative stress and mitochondrial dysfunction through activation of the Nrf2 pathway and may be a beneficial drug for the treatment of SIFHN.

Accelerating explicit solvent models of heterogeneous catalysts with machine learning interatomic potentials.

Realistically modelling how solvents affect catalytic reactions is a longstanding challenge due to its prohibitive computational cost. Typically, an explicit atomistic treatment of the solvent molecules is needed together with molecular dynamics (MD) simulations and enhanced sampling methods. Here, we demonstrate the utility of machine learning interatomic potentials (MLIPs), coupled with active learning, to enable fast and accurate explicit solvent modelling of adsorption and reactions on heterogeneous catalysts. MLIPs trained on-the-fly were able to accelerate ab initio MD simulations by up to 4 orders of magnitude while reproducing with high fidelity the geometrical features of water in the bulk and at metal-water interfaces. Using these ML-accelerated simulations, we accurately predicted key catalytic quantities such as the adsorption energies of CO*, OH*, COH*, HCO*, and OCCHO* on Cu surfaces and the free energy barriers of C-H scission of ethylene glycol over Cu and Pd surfaces, as validated with ab initio calculations. We envision that such simulations will pave the way towards detailed and realistic studies of solvated catalysts at large time- and length-scales.

Self-learning sliding mode control based on adaptive dynamic programming for nonholonomic mobile robots.

This paper proposes a self-learning sliding mode control (SlSMC) strategy with stability guarantee for the trajectory tracking of nonholonomic mobile robots (NMRs) under matched uncertainties, which improves the control performance of NMRs by optimizing the reaching law and the sliding mode surface of SMC as well as retaining the finite-time convergence and the robustness to uncertainties. In the presence of adverse factors such as skidding, slipping and environmental noise, the kinematic model of NMRs is reconstructed and an integral terminal sliding mode controller is designed for the trajectory tracking of NMRs. Then, based on the sliding mode controller, the proposed control strategy formulates the optimization of the SMC's reaching law and the sliding mode surface under stability constraints as two asynchronous optimal control problems with control constraints. Meanwhile, an online continuous-time receding-horizon optimization mechanism based on an actor-critic algorithm is proposed to solve the optimal problems asynchronously and improve online learning efficiency. The stability and the convergence of the proposed strategy are validated both in theory and simulations. Furthermore, extensive contrastive simulation results illustrate that the proposed receding horizon learning-based control strategy outperforms three recent methods in control performance. Finally, experiments of the proposed self-learning SMC strategy are carried out based on a real intelligent vehicle, and the experimental results also verify that the proposed method can meet the actual control needs of NMRs.

A comprehensive review for machine learning based human papillomavirus detection in forensic identification with multiple medical samples.

Human papillomavirus (HPV) is a sexually transmitted virus. Cervical cancer is one of the highest incidences of cancer, almost all patients are accompanied by HPV infection. In addition, the occurrence of a variety of cancers is also associated with HPV infection. HPV vaccination has gained widespread popularity in recent years with the increase in public health awareness. In this context, HPV testing not only needs to be sensitive and specific but also needs to trace the source of HPV infection. Through machine learning and deep learning, information from medical examinations can be used more effectively. In this review, we discuss recent advances in HPV testing in combination with machine learning and deep learning.

Access to unsaturated bicyclic lactones by overriding conventional C(sp3)-H site selectivity.

Transition metal catalysis plays a pivotal role in transforming unreactive C-H bonds. However, regioselective activation of distal aliphatic C-H bonds poses a tremendous challenge, particularly in the absence of directing templates. Activation of a methylene C-H bond in the presence of methyl C-H is underexplored. Here we show activation of a methylene C-H bond in the presence of methyl C-H bonds to form unsaturated bicyclic lactones. The protocol allows the reversal of the general selectivity in aliphatic C-H bond activation. Computational studies suggest that reversible C-H activation is followed by ß-hydride elimination to generate the Pd-coordinated cycloalkene that undergoes stereoselective C-O cyclization, and subsequent ß-hydride elimination to provide bicyclic unsaturated lactones. The broad generality of this reaction has been highlighted via dehydrogenative lactonization of mid to macro ring containing acids along with the C-H olefination reaction with olefin and allyl alcohol. The method substantially simplifies the synthesis of important bicyclic lactones that are important features of natural products as well as pharmacoactive molecules.

New Function of Metal-Organic Framework: Structurally Ordered Metal Promoter.

The remarkable roles of metal promoters have been known for nearly a century, but it is still a challenge to find a suitable structure model to reveal the action mechanism behind metal promoters. Herein, a new function of metal-organic frameworks (MOFs) is developed as an ideal model to construct structurally ordered metal promoters by a targeted post-modification strategy. MOFs as model not only favor clearing the real action mechanism behind metal promoters, but also can anchor one or multiple kinds of metal promoters especially noble metal promoters. Typically, the as-prepared Pd/bpy-UiO-Cu catalysts show high selectivity (>99%) toward 4-nitrophenylethane in 4-nitrostyrene hydrogenation, mainly due to the enhanced interaction between Pd nanoparticles and MOF carriers induced by Cu promoters, thus inhibiting the hydrogenation of 4-nitrophenylethane. This strategy with flexibility and universality will open up a new route to synthesize efficient catalysts with structurally ordered metal promoters.

Electron-Rich Triazine-Conjugated Microporous Polymers for the Removal of Dyes from Wastewater.

Conjugated microporous polymers (CMP) as porous functional materials have received considerable attention due to their unique structures and fascinating properties for the adsorption and degradation of dyes. Herein, a triazine-conjugated microporous polymer material with rich N-donors at the skeleton itself was successfully synthesized via the Sonogashira-Hagihara coupling by a one-pot reaction. These two polymers had Brunauer-Emmett-Teller (BET) surface areas of 322 and 435 m2g-1 for triazine-conjugated microporous polymers (T-CMP) and T-CMP-Me, respectively. Due to the porous effects and the rich N-donor at the framework, it displayed a higher removal efficiency and adsorption performance compared to cationic-type dyes and selectivity properties for (methylene blue) MB+ from a mixture solution of cationic-type dyes. Furthermore, the T-CMP-Me could quickly and drastically separate MB+ and (methyl orange) MO- from the mixed solution within a short time. Their intriguing absorption behaviors are supported by 13C NMR, UV-vis absorption spectroscopy, scanning electron microscopy, and X-ray powder diffraction studies. This work will not only improve the development of porous material varieties, but also demonstrate the adsorption or selectivity of porous materials for dyes from wastewater.