Highly stable coherent nanoprecipitates via diffusion-dominated solute uptake and interstitial ordering.

Lightweight design strategies and advanced energy applications call for high-strength Al alloys that can serve in the 300‒400 °C temperature range. However, the present commercial high-strength Al alloys are limited to low-temperature applications of less than ~150 °C, because it is challenging to achieve coherent nanoprecipitates with both high thermal stability (preferentially associated with slow-diffusing solutes) and large volume fraction (mostly derived from high-solubility and fast-diffusing solutes). Here we demonstrate an interstitial solute stabilizing strategy to produce high-density, highly stable coherent nanoprecipitates (termed the V phase) in Sc-added Al-Cu-Mg-Ag alloys, enabling the Al alloys to reach an unprecedented creep resistance as well as exceptional tensile strength (~100 MPa) at 400 °C. The formation of the V phase, assembling slow-diffusing Sc and fast-diffusing Cu atoms, is triggered by coherent ledge-aided in situ phase transformation, with diffusion-dominated Sc uptake and self-organization into the interstitial ordering of early-precipitated Ω phase. We envisage that the ledge-mediated interaction between slow- and fast-diffusing atoms may pave the way for the stabilization of coherent nanoprecipitates towards advanced 400 °C-level light alloys, which could be readily adapted to large-scale industrial production.

Seed pretreatment with brassinosteroids stimulates sunflower immunity against parasitic weed (Orobanche cumana) infection.

Broomrape (Orobanche cumana) negatively affects sunflower, causing severe yield losses, and thus, there is a need to control O. cumana infestation. Brassinosteroids (BRs) play key roles in plant growth and provide resilience to weed infection. This study aims to evaluate the mechanisms by which BRs ameliorate O. cumana infection in sunflower (Helianthus annuus). Seeds were pretreated with BRs (1, 10, and 100 nM) and O. cumana inoculation for 4 weeks under soil conditions. O. cumana infection significantly reduced plant growth traits, photosynthesis, endogenous BRs and regulated the plant defence (POX, GST), BRs signalling (BAK1, BSK1 to BSK4) and synthesis (BRI1, BR6OX2) genes. O. cumana also elevated the levels of malondialdehyde (MDA), hydroxyl radical (OH-), hydrogen peroxide (H2O2) and superoxide (O2 •-) in leaves/roots by 77/112, 63/103, 56/97 and 54/89%, as well as caused ultrastructural cellular damages in both leaves and roots. In response, plants activated a few enzymes, superoxide dismutase (SOD), peroxidase (POD) and reduced glutathione but were unable to stimulate the activity of ascorbate peroxidase (APX) and catalase (CAT) enzymes. The addition of BRs (especially at 10 nM) notably recovered the ultrastructural cellular damages, lowered the production of oxidative stress, activated the key enzymatic antioxidants and induced the phenolic and lignin contents. The downregulation in the particular genes by BRs is attributed to the increased resilience of sunflower via a susceptible reaction. In a nutshell, BRs notably enhanced the sunflower resistance to O. cumana infection by escalating the plant immunity responses, inducing systemic acquired resistance, reducing oxidative or cellular damages, and modulating the expression of BR synthesis or signalling genes.

Liver resection with two-step vascular exclusion, in situ hypothermic portal perfusion for the treatment of end-stage hepatic alveolar echinococcosis.

PURPOSE: To evaluate the safety and efficacy of two-step vascular exclusion and in situ hypothermic portal perfusion in patients with end-stage hepatic hydatidosis. METHODS: This study involved patients with advanced hepatic hydatid disease undergoing surgical treatment between 2022 and 2023, which included resection and reconstruction of the hepatic veins, inferior vena cava (IVC), and portal vein (PV). We described the technical details of liver resection and vascular reconstruction, as well as the use of two-step vascular exclusion and in situ hypothermic portal perfusion techniques during the vascular reconstruction process. RESULT: We included 7 patients with advanced hepatic hydatid disease who underwent surgical resection using two-step vascular exclusion and in situ hypothermic portal perfusion. The mean duration of surgery was 12.5 h (range, 7.5-15.0 h). The average hepatic ischemia time was 45 min (range, 25-77 min), while the occlusion time of the IVC was 87 min (range, 72-105 min). The total blood loss was 1000 milliliters (range, 500-1250 milliliters). Postoperatively, patients exhibited good recovery of liver and renal function. The mean ICU stay was 2 days (range, 1-3 days), and the mean postoperative hospital stay was 13 days (range, 9-16 days), with no Grade III or above complications observed during a mean follow-up period of 15 months (range, 9-24 months), CONCLUSION: two-step vascular exclusion and in situ hypothermic portal perfusion for surgical resection of end-stage hepatic hydatid disease is safe and effective. This significantly reduces the anhepatic time.

Upregulation of CSNK1A1 induced by ITGB5 confers to hepatocellular carcinoma resistance to sorafenib in vivo by disrupting the EPS15/EGFR complex.

Oral multitarget tyrosine kinase inhibitors (TKIs), such as sorafenib, which suppress tumor cell proliferation and tumor angiogenesis, have been approved to treat patients with hepatocellular carcinoma (HCC). Of note, only approximately 30% of patients can benefit from TKIs, and this population usually acquires drug resistance within 6 months. In this study, we intended to explore the mechanism associated with regulating the sensitivity of HCC to TKIs. We revealed that integrin subunit ß 5 (ITGB5) is abnormally expressed in HCC and contributes to decreased the sensitivity of HCC to sorafenib. Mechanistically, unbiased mass spectrometry analysis using ITGB5 antibodies revealed that ITGB5 interacts with EPS15 to prevent the degradation of EGFR in HCC cells, which activates AKT-mTOR signaling and the MAPK pathway to reduce the sensitivity of HCC cells to sorafenib. In addition, mass spectrometry analysis showed that CSNK1A1 binds to ITGB5 in HCC cells. Further study indicated that ITGB5 increased the protein level of CSNK1A1 through the EGFR-AKT-mTOR pathway in HCC. Upregulated CSNK1A1 phosphorylates ITGB5 to enhance the interaction between ITGB5 and EPS15 and activate EGFR in HCC cells. Thus, we identified a positive feedback loop between ITGB5-EPS15-EGFR-CSNK1A1 in HCC cells. This finding provides a theoretical basis for the future development of therapeutic strategies to improve the anti-HCC efficacy of sorafenib.

Melatonin ameliorates bleomycin-induced pulmonary fibrosis via activating NRF2 and inhibiting galectin-3 expression.

Pulmonary fibrosis (PF) is a chronic interstitial lung disease with no effective therapies. Galectin-3 (Gal-3), a marker of oxidative stress, plays a key role in the pathogenesis of PF. Fibroblast-myofibroblast differentiation (FMD) is an important source of fibrotic cells in PF. Previous studies showed that melatonin (MT) exerted anti-fibrotic effect in many diseases including PF through its antioxidant activity. In the present study we investigated the relationships among Gal-3, NRF2, ROS in FMD and their regulation by MT. We established an in vitro model of FMD in TGF-ß1-treated human fetal lung fibroblast1 (HFL1) cells and a PF mouse model via bleomycin (BLM) intratracheal instillation. We found that Gal-3 expression was significantly increased both in vitro and in vivo. Knockdown of Gal-3 in HFL1 cells markedly attenuated TGF-ß1-induced FMD process and ROS accumulation. In TGF-ß1-treated HFL1 cells, pretreatment with NRF2-specific inhibitor ML385 (5 µM) significantly increased the levels of Gal-3, α-SMA and ROS, suggesting that the expression of Gal-3 was regulated by NRF2. Treatment with NRF2-activator MT (250 µM) blocked α-SMA and ROS accumulation accompanied by reduced Gal-3 expression. In BLM-induced PF model, administration of MT (5 mg·kg-1·d-1, ip for 14 or 28 days) significantly attenuated the progression of lung fibrosis through up-regulating NRF2 and down-regulating Gal-3 expression in lung tissues. These results suggest that Gal-3 regulates TGF-ß1-induced pro-fibrogenic responses and ROS production in FMD, and MT activates NRF2 to block FMD process by down-regulating Gal-3 expression. This study provides a useful clue for a clinical strategy to prevent PF. Graphic abstract of the mechanisms. MT attenuated BLM-induced PF via activating NRF2 and inhibiting Gal-3 expression.

Biodegradable mulch films improve yield of winter potatoes through effects on soil properties and nutrients.

Biodegradable mulch films are recognized as a promising substitute of polyethylene (PE) films to alleviate the "white pollution". Biodegradable mulch films with optimum degradation rates increase crop yield even compared to PE films. However, the mechanisms underlying this yield-increasing effect remains elusive. In this study, three biodegradable film treatments (BFM1, BFM2 and BFM3) and one PE film treatment (PFM) were used to evaluate their effects on soil and winter potatoes, and a partial least squares path model (PLS-PM) was constructed to investigate their relationships. The degradation rates of films under different treatments were ranked as BFM3 > BFM2 >BFM1 > PFM, and presented distinctive effects on soil properties and nutrients, structure of soil bacterial community, and yield traits of winter potatoes. The PLS-PM showed that mulch treatments affected potato yield through effects on soil properties (soil water and temperature) and soil nutrients (TOC, DOC, TN and NO3--N). The disintegration of the biodegradable films decreased soil water content and temperature, and reduced the loss of soil nutrients in the topsoil at the later growth stage of winter potatoes compared to PE films. Additionally, the elevated content of soil TN and NO3--N under treatment BFM1 may play a key role in its yield-increasing effect on potatoes compared to treatments PFM and BFM2. Thus, biodegradable mulch films with proper degradation rates regulate soil TN and NO3--N through their effects on soil water and temperature, and subsequently improve the yield of winter potatoes compared to PE mulch films.

Saving 80% Polypropylene in Facemasks by Laser-Assisted Melt-Blown Nanofibers.

The ongoing coronavirus (COVID-19) pandemic requires enormous production of facemasks and related personal protection materials, thereby increasing the amount of nondegradable plastic waste. The core material for facemasks is melt-blown polypropylene (PP) fiber. Each disposable facemask consumes ∼0.7 g of PP fibers, resulting in annual global consumption and disposal of more than 1 150 000 tons of PP fibers annually. Herein, we developed a laser-assisted melt-blown (LAMB) technique to manufacture PP nanofibers with a quality factor of 0.17 Pa-1 and significantly reduced the filter's weight. We demonstrated that a standard surgical facemask could be made with only 0.13 g of PP nanofibers, saving approximately 80% of the PP materials used in commercial facemasks. Theoretical analysis and modeling were also conducted to understand the LAMB process. Importantly, nanofibers can be easily scaled up for mass production by upgrading traditional melt blown line with scanning laser-assisted melt-blown (SLAMB).

Origins of Stereospecificity and Divergent Reactivity of Pd-Catalyzed Cross Coupling with α,α-Disubstituted Alkenyl Hydrazones.

This article presents an exploration of stereospecificity and divergent reactivity of Pd-catalyzed α,α-disubstituted alkenyl hydrazones to synthesize 1,4-dienes in the Z configuration and vinylcyclopropane. We calculated the energy profiles of four α,α-disubstituted alkenyl hydrazones. The results show that the energy profiles of the whole catalytic cycle are basically the same before the syn-carbopalladation step. Subsequent syn-ß-C elimination yields skipping dienes, or direct ß-H elimination yields vinylcyclopropane. Current theoretical calculations reveal that the stereospecificity and the divergent reactivity of reactions result from the competition between syn-ß-C elimination and ß-H elimination. The C-C bond rotation and subsequent syn-ß-C elimination step control the stereospecificity of the reaction by changing the olefin stereostructure from E to Z configuration. The steric factor of α-substituted groups mediates the transformation between syn-ß-C elimination and ß-H elimination. The results are of great significance for the scientific design of substrates to achieve accurate synthesis of target products.

Cation Bridge Mediating Homo- and Cross-Coupling in Copper-Catalyzed Reductive Coupling of Benzaldehyde and Benzophenone.

A novel mechanism of organobase-mediated Brook rearrangement and C-C coupling in the copper-catalyzed reductive coupling of benzaldehyde and benzophenone is proposed. The results demonstrate that this reaction proceeds mainly through five sequential elementary steps: transmetalation, carbonyl addition, σ-bond metathesis, Brook rearrangement, and C-C coupling. The organobases played a significant role not only in forming the active catalyst but also in mediating the Brook rearrangement and chemoselectivity in homo- and cross-coupling. Brook rearrangement mediated by organobases is more favored than that without organobases. In the C-C coupling step, the cation bridge combines two O atoms with the same electronegativity to form a pre-reaction complex. Moreover, a significant charge difference is a major factor in the selectivity of carbonyl addition and C-C coupling.

Analysis of retinal microvasculature features in amblyopic eyes: A meta-analysis.

PURPOSE: This meta-analysis aimed to evaluate retinal vessel density (VD) in amblyopic patients using optical coherence tomography angiography (OCTA). METHODS: PubMed, Web of Science, Embase, and Cochrane Library databases were systematically searched for published articles comparing retinal microvasculature characteristics in patients with amblyopia and controls. Continuous variable outcomes were assessed using the mean difference (MD) with a 95% confidence interval. Review Manager Version 5.30 was used for the analysis. RESULTS: Thirteen qualified articles were pooled in this meta-analysis. Compared with controls, the foveal whole enface VD of superficial (SCP) and deep capillary plexus (DCP) of patients as measured by 3×3-mm scans were significantly lower in amblyopia eyes (MD: -1.37, P = 0.0003; MD: 1.70, P < 0.00001, respectively). Similarly, in the 6×6-mm scans, foveal whole enface VD of the SCP and DCP were remarkably lower in amblyopia eyes than in controls (MD: -2.24, P = 0.03; MD: -5.08, P = 0.04, respectively). The parafoveal VD of SCP in 3×3-mm scans (MD: -1.96, P < 0.00001) was also lower in amblyopic patients than in controls. Similarly, in 6×6-mm scans, amblyopia eyes showed a significant decrease, and a trending decrease in the parafoveal VD of the SCP (MD: -3.85, P = 0.007) and DCP (MD: -3.03, P = 0.10), respectively. For whole radial peripapillary capillary (RPC), VD was significantly reduced in amblyopic patients compared to controls (MD = -0.83, P < 0.00001). In addition, the deep foveal avascular zone (FAZ) was larger in amblyopic eyes than in the controls (MD = 0.55, P= 0.007). CONCLUSIONS: Our data suggest that whole foveal and parafoveal VD and RPC whole VD were reduced in patients with amblyopia. Moreover, our results reveal that the FAZ is larger in amblyopic patients. Consequently, OCTA may have the potential for diagnosing and monitoring patients with amblyopia.

Consistent Optimization of Blast Furnace Ironmaking Process Based on Controllability Assurance Soft Sensor Modeling.

The blast furnace ironmaking process is the core of steel manufacturing, and the optimization of this process can bring enormous economic and environmental benefits. However, previous data-driven optimization methods neglect the uncontrollability of part of the variables in the predictive modeling process, which brings great uncertainty to the optimization results and adversely affects the optimization effect. To address this problem, a consistency optimization framework based on controllability assurance soft sensor modeling is proposed. The method achieves the information extraction of uncontrollable variables in a process-supervised way, and improves the posterior distribution prediction accuracy. The method also proposes an integrated self-encoder regression module, which uses the regression to guide the encoding, realize the construction of latent features, and further improve the prediction accuracy of the model. Integrating the prediction module and the multi-objective gray wolf optimizer, the proposed model achieves the optimization of the blast furnace ironmaking process with only controllable variables as prediction model inputs while being capable of giving uncertainty estimates of the solutions. Empirical data validated the optimization model and demonstrated the effectiveness of the proposed algorithm.

Mutation of OsPIN1b by CRISPR/Cas9 Reveals a Role for Auxin Transport in Modulating Rice Architecture and Root Gravitropism.

The distribution and content of auxin within plant tissues affect a variety of important growth and developmental processes. Polar auxin transport (PAT), mainly mediated by auxin influx and efflux transporters, plays a vital role in determining auxin maxima and gradients in plants. The auxin efflux carrier PIN-FORMED (PIN) family is one of the major protein families involved in PAT. Rice (Oryza sativa L.) genome possesses 12 OsPIN genes. However, the detailed functions of OsPIN genes involved in regulating the rice architecture and gravity response are less well understood. In the present study, OsPIN1b was disrupted by CRISPR/Cas9 technology, and its roles in modulating rice architecture and root gravitropism were investigated. Tissue-specific analysis showed that OsPIN1b was mainly expressed in roots, stems and sheaths at the seedling stage, and the transcript abundance was progressively decreased during the seedling stages. Expression of OsPIN1b could be quickly and greatly induced by NAA, indicating that OsPIN1b played a vital role in PAT. IAA homeostasis was disturbed in ospin1b mutants, as evidenced by the changed sensitivity of shoot and root to NAA and NPA treatment, respectively. Mutation of OsPIN1b resulted in pleiotropic phenotypes, including decreased growth of shoots and primary roots, reduced adventitious root number in rice seedlings, as well as shorter and narrower leaves, increased leaf angle, more tiller number and decreased plant height and panicle length at the late developmental stage. Moreover, ospin1b mutants displayed a curly root phenotype cultured with tap water regardless of lighting conditions, while nutrient solution culture could partially rescue the curly root phenotype in light and almost completely abolish this phenotype in darkness, indicating the involvement of the integration of light and nutrient signals in root gravitropism regulation. Additionally, amyloplast sedimentation was impaired in the peripheral tiers of the ospin1b root cap columella cell, while it was not the main contributor to the abnormal root gravitropism. These data suggest that OsPIN1b not only plays a vital role in regulating rice architecture but also functions in regulating root gravitropism by the integration of light and nutrient signals.

Implementation of Quantum Algorithms via Fast Three-Rydberg-Atom CCZ Gates.

Multiqubit CCZ gates form one of the building blocks of quantum algorithms and have been involved in achieving many theoretical and experimental triumphs. Designing a simple and efficient multiqubit gate for quantum algorithms is still by no means trivial as the number of qubits increases. Here, by virtue of the Rydberg blockade effect, we propose a scheme to rapidly implement a three-Rydberg-atom CCZ gate via a single Rydberg pulse, and successfully apply the gate to realize the three-qubit refined Deutsch-Jozsa algorithm and three-qubit Grover search. The logical states of the three-qubit gate are encoded to the same ground states to avoid an adverse effect of the atomic spontaneous emission. Furthermore, there is no requirement for individual addressing of atoms in our protocol.

Protective effect of dimethyl itaconate against fibroblast-myofibroblast differentiation during pulmonary fibrosis by inhibiting TXNIP.

Fibroblast-myofibroblast differentiation (FMD) is a critical cellular phenotype during the occurrence and deterioration of pulmonary fibrosis (PF). FMD can increase with an elevated level of reactive oxygen species (ROS) on fibroblasts under oxidative stress. Thioredoxin-interacting protein (TXNIP) is an α-arrestin family protein that regulates the level of intracellular ROS. Nuclear factor erythroid 2-related factor 2 (Nrf2) can protect against FMD in PF. However, the relationship between Nrf2 and TXNIP in FMD remains elusive. Therefore, we established TGF-ß1-induced FMD in vitro and bleomycin (BLM)-induced mouse PF model in vivo to explore whether the activation of Nrf2 can inhibit TXNIP-mediated FMD in PF. Dimethyl itaconate (DMI) was selected to activate Nrf2. Our results showed that TXNIP was elevated and FMD was aggravated in mice lung tissues after BLM administration compared with the saline group. Inversely, Nrf2 decreased TXNIP expression and alleviated FMD in PF. In vitro, TXNIP overexpression enhanced FMD and increased the level of ROS. In contrast, TXNIP deficiency by small interfering RNA (siRNA) attenuated TGF-ß1-induced FMD and reduced ROS. An increase in ROS by H2 O2 can upregulate TXNIP expression. Moreover, Nrf2 also inhibited TGF-ß1-induced FMD and the increase of ROS, with reducing expression of TXNIP, and the inhibitory effect was better than TXNIP siRNA. These results suggest that activation of Nrf2 by DMI can protect against PF via inhibiting TXNIP expression. Our study may provide new therapeutic targets and treatment approaches for PF.

Mitochondria transfer from early stages of erythroblasts to their macrophage niche via tunnelling nanotubes.

Adult erythropoiesis entails a series of well-coordinated events that produce mature red blood cells. One of such events is the mitochondria clearance that occurs cell-autonomously via autophagy-dependent mechanisms. Interestingly, recent studies have shown mitochondria transfer activities between various cell types. In the context of erythropoiesis, macrophages are known to interact closely with the early stages of erythroblasts to provide a specialized niche, termed erythroblastic islands (EBI). However, whether mitochondria transfer can occur in the EBI niche has not been explored. Here, we report that mitochondria transfer in the EBI niche occurs in vivo. We observed mitochondria transfer activities from the early stages of erythroblasts to macrophages in the reconstituted in vitro murine EBI via different modes, including tunnelling nanotubes (TNT). Moreover, we demonstrated that Wiskott-Aldrich syndrome protein (WASp) in macrophages mediates TNT formation and mitochondria transfer via the modulation of F-actin filamentation, thus promoting mitochondria clearance from erythroid cells, to potentially enhance their differentiation. Taken together, our findings provide novel insight into the mitochondria clearance machineries that mediate erythroid maturation.

Screening for upper gastrointestinal cancers with magnetically controlled capsule gastroscopy: a feasibility study.

BACKGROUND: The medical consortium is an intensive and disease-specific association that integrates tertiary public hospitals and medical examination centers in China. We aimed to evaluate the feasibility of the medical consortium for screening upper gastrointestinal (GI) cancers (MCSC) by magnetically controlled capsule gastroscopy (MCCG). METHODS: 6627 asymptomatic subjects underwent MCCG as part of health check-ups in the MCSC between March and November 2018. Relevant clinical data were collected and analyzed. RESULTS: The MCSC detected 32 patients with upper GI cancer (0.48 %) confirmed by pathology. The detection rate of early gastric cancer was 16.67 % (4 /24). Gastric polyps, ulcers, and submucosal tumors were found in 15.54 %, 3.76 %, and 3.17 % of subjects, respectively. The whole GI preparation and operation process were well tolerated. CONCLUSIONS: The MCSC was a feasible model for upper GI cancer screening, especially for asymptomatic subjects. Further prospective studies with better operational quality control are warranted.

Activated AMPK by metformin protects against fibroblast proliferation during pulmonary fibrosis by suppressing FOXM1.

Pulmonary fibrosis (PF) is a progressive and devastating lung disease of unknown etiology, excessive fibroblast proliferation serves as a key event to promote PF. Transcription factor forkhead box M1 (FOXM1) is not only a well-known proto-oncogene, but also an essential driver of cell proliferation. Recently, 5'-AMP-activated protein kinase (AMPK) is reported to reduce the incidence of PF. However, it remains elusive whether have an underlying relationship between AMPK and FOXM1 in fibroblast proliferation-mediated PF. Here, the progression of lung fibroblast proliferation and the expression levels of AMPK and FOXM1 were observed by intratracheally instilled of bleomycin (BLM) and intraperitoneal injection of metformin in C57BL/6 J mice. Meanwhile, human fetal lung fibroblast1 (HFL1) cells were respectively treated with AMPK activator metformin or AMPK inhibitor Compound C, or FOXM1 depletion by transfected small interfering RNA (siRNA) to unveil roles of AMPK, FOXM1 and the link between them on platelet-derived growth factor (PDGF)-induced fibroblast proliferation. Our results demonstrated that AMPK activated by metformin could down-regulate FOXM1 and alleviate BLM-induced mouse PF model. In vitro, activation of AMPK attenuated PDGF-induced fibroblast proliferation accompanied by the down-regulation of FOXM1. In contrast, inhibition of AMPK enhanced PDGF-induced fibroblast proliferation along with activating FOXM1. These findings suggest that AMPK can ameliorate the progression of fibroblast proliferation during PF via suppressing the expression of FOXM1 and provide new insight into seek PF treatment approaches.

Mechanism of iron complexes catalyzed in the N-formylation of amines with CO2 and H2: the superior performance of N-H ligand methylated complexes.

CO2 hydrogenation into value-added chemicals not only offer an economically beneficial outlet but also help reduce the emission of greenhouse gases. Herein, the density functional theory (DFT) studies have been carried out on CO2 hydrogenation reaction for formamide production catalyzed by two different N-H ligand types of PNP iron catalysts. The results suggest that the whole mechanistic pathway has three parts: (i) precatalyst activation, (ii) hydrogenation of CO2 to generate formic acid (HCOOH), and (iii) amine thermal condensation to formamide with HCOOH. The lower turnover number (TON) of a bifunctional catalyst system in hydrogenating CO2 may attribute to the facile side-reaction between CO2 and bifunctional catalyst, which inhibits the generation of active species. Regarding the bifunctional catalyst system addressed in this work, we proposed a ligand participated mechanism due to the low pKa of the ligand N-H functional in the associated stage in the catalytic cycle. Remarkably, catalysts without the N-H ligand exhibit the significant transfer hydrogenation through the metal centered mechanism. Due to the excellent catalytic nature of the N-H ligand methylated catalyst, the N-H bond was not necessary for stabilizing the intermediate. Therefore, we confirmed that N-H ligand methylated catalysts allow for an efficient CO2 hydrogenation reaction compared to the bifunctional catalysts. Furthermore, the influence of Lewis acid and strong base on catalytic N-formylation were considered. Both significantly impact the catalytic performance. Moreover, the catalytic activity of PNMeP-based Mn, Fe and Ru complexes for CO2 hydrogenation to formamides was explored as well. The energetic span of Fe and Mn catalysts are much closer to the precious metal Ru, which indicates that such non-precious metal catalysts have potentially valuable applications.

New cytotoxic dichapetalins in the leaves of Phyllanthus acidus: Identification, quantitative analysis, and preliminary toxicity assessment.

The young leaves of Phyllanthus acidus (Euphorbiaceae) are commonly used as edible vegetables in Indonesia, Thailand, and India, and their water infusions as dieting aids for people trying to remain slim. However, it is regarded as a poisonous plant in Malaya, and current researches are insufficient to provide a conclusion on its toxicity and safety under large doses. In this study, we firstly found that the refined nonpolar extracts of P. acidus leaves showed significant cytotoxic effect against BEAS-2B and L02 normal cell lines with IC50 values of 2.15 and 1.64 mg/mL, respectively. Further bioactivity-guided isolation produced four new rare dichapetalins (pacidusins A-D) from the most active fraction. Their structures including absolute configurations were elucidated by extensive spectroscopic data and X-ray diffraction analysis. All the isolated dichapetalins exhibited moderate cytotoxicity against, BEAS-2B and L02 normal cell lines with IC50 values ranging from 12.44 to 22.55 µM, as well as five human cancer cell lines with IC50 values ranging from 3.38 to 22.38 µM. Furthermore, the content of the main dichapetalins in the leaves were determined by analytical HPLC, which showed that the leaves contained a very high amount of the four isolated dichapetalins with a total yield of 0.488 mg/g of dry plant material. These toxic dichapetalins may lead to adverse health effects in higher doses. Our findings indicate that the dichapetalin containing leaves may not be suitable for consumption in large quantities as food, but demonstrate their potency as anti-cancer agents for new drug discovery.