Copper-Catalyzed Enantioselective Hydrophosphorylation of Unactivated Alkynes.

P-stereogenic phosphorus compounds are essential across various fields, yet their synthesis via enantioselective P-C bond formation remains both challenging and underdeveloped. We report the first copper-catalyzed enantioselective hydrophosphorylation of alkynes, facilitated by a newly designed chiral 1,2-diamine ligand. Unlike previous methods that rely on kinetic resolution with less than 50% conversion, our approach employs a distinct dynamic kinetic asymmetric transformation mechanism, achieving complete conversion of racemic starting materials. This reaction is compatible with a broad range of aromatic and aliphatic terminal alkynes, producing products with high yields (up to 95%), exclusive cis selectivity, and exceptional regio- and enantioselectivity (> 20:1 r.r. and up to 96% ee). The resulting products were further transformed into a diverse array of enantioenriched P-stereogenic scaffolds. Preliminary mechanistic studies were conducted to elucidate the reaction details.

Fine-scale monitoring of catkins reveals an association between catkin concentration and plant community characteristics and microclimate.

Catkins, as a significant source of plant-caused pollution, disrupts daily human activities and industrial processes. Despite their impact, catkins have not been included in official environmental quality monitoring indicators, leading to a deficiency in scientifically rigorous collection and monitoring methodologies, as well as a lack of ecological prevention and management strategies. In this study, we introduced a fine-scale monitoring approach for catkins. Qualitative and quantitative relationships between catkin concentrations, plant community characteristics and microclimate factors were elucidated by analyzing on-site catkin concentration data from 33 representative plant communities in Beijing. Furthermore, we summarized the ecological strategies for the prevention and management of these catkins. The results indicated that (1) TS (three-dimensional green volume of trees in the catkin source layer), SB (three-dimensional green volume of shrubs in the catkin barrier layer), GB (three-dimensional green volume of ground cover plants in the catkin barrier layer), T (three-dimensional green volume of trees in the whole plant community), W (three-dimensional green volume of the whole plant community), species diversity, and relative air humidity were key plant community characteristics and microclimate factors influencing catkin concentration. Among these factors, TS, T, W, and relative air humidity showed a significant positive correlation with catkin concentration, while SB, GB, and species diversity exhibited a significant negative correlation with catkin concentration. (2) All seven key factors exhibited nonlinear relationships with catkin concentration. (3) TS served as the primary deciding factor for catkin concentration within the plant community. When TS > 744.0755 m3, the secondary decision factor for catkin concentration was GB. Otherwise, the determinants were SB and species diversity. The results showed that enhancing tree species diversity, enhancing the three-dimensional green volume of shrubs and ground cover plants, and increasing air humidity were practical means to facilitate the sedimentation of catkins. The measures used to obstruct catkins vary depending on the TS. When catkin source plants are abundant within a plant community, it is advisable to prioritize increasing ground cover plants. Conversely, when fewer sources of such plants exist, emphasis can be placed on augmenting mid-layer shrubs and diversifying plant species. These findings provide a scientific foundation for the planting design and stock optimization of communities containing catkin source plants.

[Identification of key ecological restoration areas for abandoned mining sites in Handan City: Based on ecological function and spatial importance]. / é‚¯éƒ¸å¸‚çŸ¿ä¸šåºŸå¼ƒåœ°çš„ç”Ÿæ€ä¿®å¤å ³é”®åŒºè¯†åˆ«: 基于生态功能与空间的重要性.

The identification of key areas for ecological restoration in national land space is crucial for anchoring the bottom line of urban ecological security. As the core of ecological restoration in many resource-based cities, the zoning construction of abandoned mining sites has practical significance. We classified the abandoned mining sites in Handan City based on ecological functions and spatial importance, aiming to provide theoretical support for the orderly development of urban ecological restoration work. In terms of research framework, we proposed to overlay the importance of ecological protection at the functional level and the ecological security pattern at the spatial level, in order to obtain more accurate identification results of key ecological restoration areas at the urban scale. During the study process, we selected four indicators that fitting the regional characteristics of water conservation, soil conservation, biodiversity conservation, and soil erosion sensitivity for ecological protection importance evaluation, and selected the MSPA-Conefor-SPCA-MCR-circuit theory to construct the ecological security pattern. The results showed that 73 out of the remaining 204 abandoned mining sites belonged to the key ecological restoration areas, with a total area of 1500.9 hm2 in Handan City, which were mainly concentrated in the regions of Gushan, Fenghuangshan, and Fushan mountains. These regions had serious ecological and enviornmental problems, but with enormous potential value. Actively seeking site transformation on the basis of simple greening to extend the value chain and industrial chain of mining ecological restoration may become a more important goal in these regions.

Reconstruction and Solidification of Dion-Jacobson Perovskite Top and Buried Interfaces for Efficient and Stable Solar Cells.

Quasi-two-dimensional (Q-2D) perovskites show great potential in the field of photonic and optoelectronic device applications. However, defects and local lattice dislocation still limit performance and stability improvement by nonradiative recombination, unpreferred phase distribution, and unbonded amines. Here, a low-temperature synergistic strategy for both reconstructing and solidifying the perovskite top and buried interface is developed. By post-treating the 1,4-phenylenedimethanammonium (PDMA) based (PDMA)MA4Pb5I16 films with cesium acetate (CsAc) before thermal annealing, a condensation reaction between R-COO- and -NH2 and ion exchange between Cs+ and MA+ occur. It converts the unbonded amines to amides and passivates uncoordinated Pb2+. Meanwhile, it adjusts film composition and improves the phase distribution without changing the out-of-plane grain orientation. Consequently, performance of 18.1% and much-enhanced stability (e.g., stability for photo-oxygen increased over 10 times, light-thermal for T90 over 4 times, and reverse bias over 3 times) of (PDMA)MA4Pb5I16 perovskite solar cells are demonstrated.

[A new secoiridoid from Cornus officinalis].

The chemical constituents from Cornus officinalis were isolated and purified by various techniques such as macroporous adsorption resin, silica gel, octadecylsilyl(ODS), Sephadex LH-20 column chromatography and preparative high-performance liquid chromatography(HPLC). The structures of the isolates were determined by a combination of spectroscopic techniques such as high-resolution electrospray ionization mass spectrometry(HR-ESI-MS), one-dimensional(1D) and two-dimensional(2D) nuclear magnetic resonance(NMR) spectroscopy. Ten compounds were isolated from the aqueous extract of C. officinalis and identified as(±)-cornuscone(1),(-)-(Z)-4-hydroxy-3-methoxyphenylpropene 4-O-ß-L-xylopyranosyl-(1→6)-ß-D-glucopyranoside(2), kaempferol 3-O-ß-D-glucopyranoside(3), kampferol(4), myricetin(5), trifolin(6), quercetin 3-O-ß-D-glucopyranoside(7), quercetin 3-O-ß-D-glucuronide-6″-methyl ester(8), quercetin 3-O-ß-D-glucuronide-6″-ethyl ester(9) and pyrogallol(10). Compound 1 is a new secoiridoid, named(±)-cornuscone with a rare methyl substitution at the C-1 position. The anti-inflammatory activity of 1 was evaluated in lipopolysaccharide(LPS)-induced RAW264.7 cells in mice. The results showed the median inhibition concentration(IC_(50)) of 1 was(31.15±1.29)µmol·L~(-1), which demonstrated that the anti-inflammatory activity of 1 was significantly superior to that of indomethacin [IC_(50) value of(48.32±1.66)µmol·L~(-1)].

[Research progress on C_(20)-diterpenoid alkaloids and their bioactivities in Ranunculaceae].

C_(20)-diterpenoid alkaloids are mainly distributed in plants of genus Aconitum, Delphinium, and Consolida in the Ranunculaceae. Their chemical structures are mainly categorized into nine types such as atisines, denudatines, hetidines, and hetisines. Bioactivity studies have shown that C_(20)-diterpenoid alkaloids have exhibited superior anti-tumor, analgesic, antiarrhythmic, and anti-inflammatory effects. In this review, the chemical structures and biological activities of 190 C_(20)-diterpenoid alkaloids reported in the Ranunculaceae from 2002 to the present were summarized, so as to provide a reference for the subsequent research on C_(20)-diterpenoid alkaloids in plants of Ranunculaceae.

New polycyclic polyprenylated acylphloroglucinols with antidepressant activities from Hypericum perforatum L.

Six new polycyclic polyprenylated acylphloroglucinols (PPAPs), hyperidiones A-F (1-6), were obtained from Hypericum perforatum L. Their structures were characterized via extensive spectroscopic analyses, the circular dichroism data of the in situ formed [Mo2(OCOCH3)4] complexes, the nuclear magnetic resonance calculation with DP4 + probability analysis, and the calculated electronic circular dichroism (ECD) spectra. Compounds 1-6 are bicyclic polyprenylated acylphloroglucinols with a major bicyclo[3.3.1]nonane-2,4,9-trione skeleton. Notably, compound 1 is a rare PPAP with a hydroperoxy group, and a plausible biosynthetic pathway for 1 was proposed. Compounds 4 and 6 exhibited significant neuroprotective effects under 10 µM against corticosterone (CORT)-injured SH-SY5Y cells. Furthermore, compound 4 demonstrated a noteworthy antidepressant effect at the dose of 5 mg/kg in the tail suspension test (TST) of mice, which was equivalent to 5 mg/kg of fluoxetine. And it potentially exerted an antidepressant effect through the hypothalamic-pituitary-adrenal (HPA) axis.

C-Phycocyanin improves the quality of goat oocytes after in vitro maturation and vitrification.

In vitro maturation (IVM) and cryopreservation of goat oocytes are important for establishing a valuable genetic bank for domesticated female animals and improving livestock reproductive efficiency. C-Phycocyanin (PC) is a Spirulina extract with antioxidant, antiinflammatory, and radical scavenging properties. However, whether PC has positive effect on goat oocytes IVM or developmental competence after vitrification is still unknown. In this study, we found that first polar body extrusion (n = 293), cumulus expansion index (n = 269), and parthenogenetic blastocyst formation (n = 281) were facilitated by adding 30 µg/mL PC to the oocyte maturation medium when compared with the control groups and that supplemented with 3, 10, 100 or 300 µg/mL PC (P < 0.05). Although PC supplementation did not affect spindle formation or chromosome alignment (n = 115), it facilitated or improved cortical granules migration (n = 46, P < 0.05), mitochondria distribution (n = 39, P < 0.05), and mitochondrial membrane potential (n = 46, P < 10-4). Meanwhile, supplementation with 30 µg/mL PC in the maturation medium could significantly inhibit the reactive oxygen species accumulation (n = 65, P < 10-4), and cell apoptosis (n = 42, P < 0.05). In addition, PC increased the oocyte mRNA levels of GPX4 (P < 0.01), and decreased the mRNA and protein levels of BAX (P < 0.01). Next, we investigated the effect of PC supplementation in the vitrification solution on oocyte cryopreservation. When compared with the those equilibrate in the vitrification solution without PC, recovered oocytes in the 30 µg/mL PC group showed higher ratios of normal morphology (n = 85, P < 0.05), survival (n = 85, P < 0.05), first polar body extrusion (n = 62, P < 0.05), and parthenogenetic blastocyst formation (n = 107, P < 0.05). Meanwhile, PC supplementation of the vitrification solution increased oocyte mitochondrial membrane potential (n = 53, P < 0.05), decreased the reactive oxygen species accumulation (n = 73, P < 0.05), promoted mitochondria distribution (n = 58, P < 0.05), and inhibited apoptosis (n = 46, P < 10-3). Collectively, our findings suggest that PC improves goat oocyte IVM and vitrification by reducing oxidative stress and early apoptosis, which providing a novel strategy for livestock gamete preservation and utilization.

Integrated assessment of the pollution and risk of heavy metals in soils near chemical industry parks along the middle Yangtze River.

Industrialization in riparian areas of critical rivers has caused significant environmental and health impacts. Taking eight industrial parks along the middle Yangtze River as examples, this study proposes a multiple-criteria approach to investigate soil heavy metal pollution and associated ecological and health risks posed by industrial activities. Aiming at seven heavy metals, the results show that nickel (Ni), cadmium (Cd), and copper (Cu) exhibited the most significant accumulation above background levels. The comprehensive findings from Pearson correlation analysis, cluster analysis, principal component analysis, and industrial investigation uncover the primary sources of Cd, arsenic (As), mercury (Hg), and lead (Pb) to be chemical processing, while Ni and chromium (Cr) are predominantly derived from mechanical and electrical equipment manufacturing. In contrast, Cu exhibits a broad range of origins across various industrial processes. Soil heavy metals can cause serious ecological and carcinogenic health risks, of which Cd and Hg contribute to >70 % of the total ecological risk, and As contributes over 80 % of the total health risk. This study highlights the importance of employing multiple mathematical and statistical models in determining and evaluating environmental hazards, and may aid in planning the environmental remediation engineering and optimizing the industry standards.

Arabidopsis Leaf Chloroplasts Have a Specific Sphingolipidome.

Sphingolipids are ubiquitous in eukaryotes and certain prokaryotes, where they serve as vital components of biological membranes and bioactive molecules. Chloroplasts have complex membrane structures that play crucial roles in photosynthesis, but their specific sphingolipidome remains unreported. In this study, we used liquid chromatography-mass spectrometry (LC-MS/MS) to analyze the sphingolipidome of purified Arabidopsis thaliana chloroplasts. We detected 92 chloroplast sphingolipids. The chloroplast sphingolipidome differed from total leaf (TL) samples, with a higher content of free long-chain bases and hydroxyceramides and a greater proportion of complex sphingolipids with 16C fatty acid (FA) forms. Notably, chloroplast glucosylceramides were predominantly the d18:1 h16:0 and t18:1 h16:0 forms rather than the 24C FA form found in TL and other cellular structures. Comparing the sphingolipidomes of different cellular structures underscores the inhomogeneity of the intracellular distribution of sphingolipids. This provides a robust reference for further elucidating the function of sphingolipids in plant cells.

One-pot chitin pulping using recyclable superbase-based protic ionic liquid.

The application of ionic liquids and deep eutectic solvents offers a promising opportunity for a more environmentally friendly and straightforward chitin purification process from crustacean shells. Nonetheless, the insufficient recyclability of these ionic solvents poses a challenge to the long-term sustainability of such extraction methods. Thus, there is a strong imperative to focus on employing easily recyclable ionic liquids for chitin isolation, enhancing the overall sustainability of the process. In this investigation, a direct chitin purification procedure that utilized pulping liquors consisting of the superbase-based protic ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate and its precursor, acetic acid, was developed. It was demonstrated that these pulping liquors were capable of simultaneously deproteinate and demineralize shrimp shells to generate chitins with higher purity, degree of N-acetylation and crystallinity than commercially obtained chitin. More significantly, the pulping liquors can be recycled to their pure form in high quantity by simple distillation under reduced pressure, allowing the reuse of these mixtures, which give chitin of nearly identical purity.

PlantMetSuite: A User-Friendly Web-Based Tool for Metabolomics Analysis and Visualisation.

The advancement of mass spectrometry technologies has revolutionised plant metabolomics research by enabling the acquisition of raw metabolomics data. However, the identification, analysis, and visualisation of these data require specialised tools. Existing solutions lack a dedicated plant-specific metabolite database and pose usability challenges. To address these limitations, we developed PlantMetSuite, a web-based tool for comprehensive metabolomics analysis and visualisation. PlantMetSuite encompasses interactive bioinformatics tools and databases specifically tailored to plant metabolomics data, facilitating upstream-to-downstream analysis in metabolomics and supporting integrative multi-omics investigations. PlantMetSuite can be accessed directly through a user's browser without the need for installation or programming skills. The tool is freely available and will undergo regular updates and expansions to incorporate additional libraries and newly published metabolomics analysis methods. The tool's significance lies in empowering researchers with an accessible and customisable platform for unlocking plant metabolomics insights.

Siliceous Origin of the Cambrian Qiongzhusi Formation Shale in the Middle Part of the Upper Yangtze Platform: Significance of Organic Matter Enrichment.

The early Cambrian Qiongzhusi Formation shale is rich in organic matter and is a high-quality marine Source rock. However, the origin of Qiongzhusi Formation siliceous rocks is unknown, and the role of siliceous rocks in the process of organic matter enrichment or preservation is also lacking. This study combines thin section, scanning electron microscopy, SEM/EDS, major and trace element analysis, and N2 adsorption experiments to analyze and evaluate the shale of the Qiongzhusi Formation in the central region of the Sichuan Basin. The quartz types in the shale of the Qiongzhusi Formation are divided into four types, namely, bioclastic siliceous rocks, terrestrial detrital quartz, siliceous microcrystalline quartz particles, and microcrystalline quartz aggregates; at the same time, according to petrographic and geochemical parameters, the content of authigenic quartz in Qiongzhusi Formation shale decreases from top to bottom, and terrigenous detrital quartz tends to increase, and biogenic silicon accounts for the majority of authigenic quartz components; autogenous quartz has a positive impact on the pore structure of shale, providing sufficient pore space for the development of organic pores and protecting the internal pore network by forming intergranular pores as rigid frameworks. At the same time, it plays a crucial role in the enrichment and preservation of organic matter.

Resveratrol inhibits oxidative damage in lungs of heat-stressed broilers by activating Nrf2 signaling pathway and autophagy.

The purpose of this study was to investigate the effects of resveratrol on heat stress-induced lung injury in broilers and the mechanism underlying this process. Sixty two-week-old SPF BWEL broilers were randomly divided into the heat stress group (HS), resveratrol group (heat stress + 400 mg/kg resveratrol), and the control group after one week of feeding, with 20 chickens in each group. Broilers in the control group were reared at 23 ± 2 â„ƒ. Those in the HS and resveratrol group were reared under heat stress (35 â„ƒ ± 2 â„ƒ) for 8 h/day for seven days. Broilers in the resveratrol group were fed a diet supplemented with 400 mg/kg resveratrol two days before the start of the experiment. The feeding was continued for nine days. The results showed that HS decreased body weight (BW), average daily feed intake (ADFI), average daily gain (ADG), and lung weight. It, however, increased the lung index, induced lung congestion, and promoted infiltration of inflammatory cells to the lung. Resveratrol improved growth performance and inhibited heat stress-induced lung damage. Compared with broilers in the control group, the expression of nuclear factor erythroid 2-related factor 2 (Nrf2), NAD(P)H quinone oxidoreductase 1 (NQO1), heme oxygenase-1 (HO-1), Beclin-1, LC3 Ⅰ, and LC3 Ⅱ genes in the lung of heat-stressed broilers was significantly lower. The levels of kelch-like ECH-associated protein 1 (Keap1), NQO1, and HO-1 showed a similar trend with gene expressions. Immunofluorescence indicated that HS inhibited the expression of Nrf2 and LC3B proteins. Finally, the ratio of LC3 Ⅱ/LC3 Ⅰ was also significantly lower in the HS group. Further analyses revealed that resveratrol supplements in feeds enhanced antioxidation in the lung by activating the Nrf2 signaling pathway and autophagy. In conclusion, HS causes oxidative damage and inhibits autophagy in broilers. However, resveratrol protects against lung injury by alleviating oxidative stress and enhancing autophagy.

Copper-Catalyzed Dynamic Kinetic Asymmetric P-C Coupling of Secondary Phosphine Oxides and Aryl Iodides.

Transition-metal-catalyzed enantioselective P-C cross-coupling of secondary phosphine oxides (SPOs) is an attractive method for synthesizing P-stereogenic phosphorus compounds, but the development of such a dynamic kinetic asymmetric process remains a considerable challenge. Here we report an unprecedented highly enantioselective dynamic kinetic intermolecular P-C coupling of SPOs and aryl iodides catalyzed by copper complexes ligated by a finely modified chiral 1,2-diamine ligand. The reaction tolerates a wide range of SPOs and aryl iodides, affording P-stereogenic tertiary phosphine oxides (TPOs) in high yields and with good enantioselectivity (average 89.2 % ee). The resulting enantioenriched TPOs were transformed into structurally diverse P-chiral scaffolds, which are highly valuable as ligands and catalysts in asymmetric synthesis.

Stelleratenoids A-F, macrocyclic daphnane orthoesters with anti-HIV activity from the roots of Stellera chamaejasme L.

Six undescribed macrocyclic daphnane orthoesters, stelleratenoids A-F (1-6), were isolated from the roots of Stellera chamaejasme L. Their structures were elucidated by extensive spectroscopic analyses, including HRESIMS and NMR spectra. Compound 1 features an unusual terminal double bond at C-2/C-19 in the 1α-alkyldaphnane lactone skeleton. Compounds 2-4 are unique in the presence of different long chain fatty acyl groups. Compounds 5 and 6 are unique examples of modified macrocyclic daphnane diterpenoids. All the isolates were evaluated for anti-HIV activity in MT-2 cells. Among them, compounds 1, 5 and 6 exhibited highly potent anti-HIV activity with EC50 values of 66.70, 10.62 and 55.10 nM, respectively, possessing high potential to develop new anti-HIV drugs.

Acetaminophen-induced hepatotoxicity predominantly via inhibiting Nrf2 antioxidative pathway and activating TLR4-NF-κB-MAPK inflammatory response in mice.

To explore the action time and molecular mechanism underlying the effect of acetaminophen (APAP) on liver injury. APAP was used to establish drug-induced liver injury (DILI) model in mice. Mice in the model group were intraperitoneally injected 300 mg/kg APAP for 6, 12, and 24 h respectively, and control group mice were given the same volume of normal saline. The mice were anesthetized through intravenous injection of sodium pentobarbital at 6, 12, and 24 h after APAP poisoning. Analysis of ALT, AST and ALP in serum, liver histopathological observation, oxidative damage and western blot were performed. The livers in APAP exposed mice were pale, smaller, with a rough texture, and poorly arranged cells. Lesions, large areas of hyperemia, inflammation, swelling, poorly cell arrangement, necrosis, and apoptosis of liver cells were obvious in the liver tissue sections. Serum ALT, AST and ALP levels were significantly enhanced at 12 h of APAP adminstration mice than that of in control group mice (P＜0.05). The histopathological alterations and proinflammatory cytokines (IL-1ß, TNF-α and IL-6) levels were most severe at 12 h of APAP-induced hepatotoxicity. APAP treatment induced oxidative stress by decreasing hepatic activities of superoxide dismutase (SOD) and glutathione (GSH) (P＜0.05), and enhancing malondialdehyde (MDA) content (P＜0.05). Moreover, APAP inhibited erythroid 2-related factor 2 (Nrf2) antioxidative pathway with decreased of Nrf2 and HO-1 proteins levels. Furthermore, APAP aggravated the activation of NLRP3 inflammasome by increasing of NLRP3, caspase-1, ASC, IL-1ß and IL-18 proteins levels. Finally, APAP further significantly activated the toll-like receptor 4 (TLR4), nuclear factor-kappa B (NF-κB) and mitogen-activated protein kinases (MAPKs) signaling pathways. This study demonstrated that APAP-induced hepatotoxicity by inhibiting of Nrf2 antioxidative pathway and promoting TLR4-NF-κB-MAPK inflammatory response and NLRP3 inflammasome activation.

mRNA 3' -UTR-mediate translational control through PAS and CPE in sheep oocyte.

In oocytes, the cytoplasmic polyadenylation and maternal mRNAs translation is regulated by cis-elements, including polyadenylation signal (PAS) and cytoplasmic polyadenylation element (CPE) in 3'-UTR. Recent studies illustrate non-canonical polyadenylation mechanisms of translational regulation in mouse oocytes, which is different from that in Xenopus oocytes. However, it is still unclear if this regulation in rodent oocytes functions in the domestic animal oocyte. Here, by using sheep as an animal model, we cloned the 3'-UTRs of Cpeb1 or Btg4 and ligated it into the pRK5-Flag-Gfp vector. Variant numbers and positions of PASs and CPEs within the 3'-UTRs were constructed to detect their effects on translational control. After in vitro-transcription and microinjection into sheep fully grown germinal vesicle stage oocytes, the expression efficiency of mRNAs was detected by the GFP and flag expression. Our results show that: (i) PAS located at the proximal end of 3'-UTR can mediate the translation of the maternal mRNAs, as long as they locate far from CPEs; (ii) The proximal PAS has higher efficiency in regulating transcription than the distal one; (iii) increase of PAS number can promote the translational activity more efficiently; (iv) a single CPE located close to PAS (<50 bp) in 3'-UTRs of Cpeb1 or Btg4 could partially repress translation. In 3'-UTRs of Btg4, two CPEs have a higher inhibitory effect, and three CPEs can completely inhibit mRNA translation. These results confirm the existence of the non-canonical mechanism in domestic animal oocytes.