The reductive amination for the preparation of secondary amine derivatives under mild condition is a significative assignment in the chemistry community. Herein, two atomically precise inorganic Ru-containing polyoxomolybdates, (NH4)2Na6H4[Ru2Mo14O52]·27H2O (Ru2Mo14) and (NH4)2Na4H2[Ru2Mo16O56]·22H2O (Ru2Mo16), are successfully isolated from identical reactants within a wide temperature range (30-90 °C). Interestingly, two clusters present the same olive-shaped structures with a dinuclear ruthenium unit in the center. Both the Ru2Mo14 and Ru2Mo16 manifested high catalytic activities for the one-pot reductive amination reaction under mild condition. Noteworthy, Ru2Mo16 served as heterogeneous catalyst exhibiting outstanding catalytic performance in the synthesis of N-benzylaniline with 99% yield, and the turnover number (TON) and turnover frequency (TOF) are 4950 and 825 h-1 respectively. Ru2Mo16, as a heterogeneous catalyst in reductive amination, can not only be extended to various secondary amine derivatives, but also maintain catalytic activity and structural stability for five consecutive times. This strategy inaugurates a new avenue to explore Ru-containing polyoxometalates catalysts in the efficient synthesis of high-value chemicals.
Five undescribed lignans (1-5), 1 - 5 ), along with sixteen known lignans (6-21), 6 - 21 ), were isolated from the roots of Anthriscus sylvestris using small molecule accurate recognition technology (SMART). The structures of the isolated compounds were determined by comprehensive spectroscopic analyses, and the absolute configurations of compounds 3 - 5 were elucidated by comparison of their calculated and experimental ECD spectra. Compounds 5 , 14-15,- 15 , 19 , and 21 exhibited significantly inhibitory effects against hypoxia-stimulated abnormal proliferation of pulmonary arterial smooth muscle cells (PASMCs). Moreover, compounds 5 , 14-15,- 15 , 19 , and 21 can significantly restore expression of expression of PASMCs proliferation-related protein, including alpha-SMA, PCNA, P27, and CyclinD3, which are closely related to cell proliferation.
BACKGROUND:Asthma poses a significant global health challenge, characterized by increasing prevalence and treatment complexities. Although Ephedrae Herba has long been used in asthma therapy, its pharmacological basis and mechanism of action remain unclear. PURPOSE:This study aimed to clarify the protective effects of pollenin B (PolB), a compound extracted from Ephedrae Herba, in asthmatic mice and to thoroughly explore its possible action pathways and molecular mechanisms. This study supplements pharmacological research on the anti-asthmatic effects of Ephedrae Herba and provides more information for the development of novel and highly effective drugs for the treatment of asthma. METHODS:An ovalbumin (OVA)-induced asthma model was used to evaluate the effects of PolB on asthma symptoms and lung histopathology. Furthermore, cytokine profiles in the serum and bronchoalveolar lavage fluid (BALF), immune cell populations, and serum metabolomics data were analyzed to identify the pathways involved in PolB activity. PPAR-γ was identified as a key target, and its interaction with PolB was confirmed by surface plasmon resonance (SPR) analysis. A PPAR-γ inhibitor (T0070907) was administered in vivo, and combined PPAR-γ agonist (rosiglitazone)/inhibitor (T0070907) assays were conducted in vitro to validate the mechanisms involved. RESULTS:PolB improved asthma symptoms, modulated cytokine levels in the serum and BALF, modulated immune cells, and influenced arachidonic acid metabolism. Further mechanistic exploration indicated that PolB mitigated airway inflammation by regulating arachidonic acid metabolism and the JAK-STAT pathway via PPAR-γ. CONCLUSION:PolB exerts anti-asthmatic effects via PPAR-γ-mediated regulation of key pathways. These findings not only enrich modern pharmacological research on the anti-asthmatic properties of Ephedrae Herba but also deepen our understanding of asthma pathogenesis, thus providing new insights into the optimization of asthma prevention and treatment.
Selective oxidation of benzylic C(sp3)-H bonds to ketones is critical to the production of fine chemicals but typically requires toxic/precious metal catalysts under harsh conditions. While iron-based complexes have recently served as catalysts for photocatalytic C-H bond activation, most systems operate via homogeneous catalysis. Developing a light-driven strategy under visible light with O2 as an oxidant is of major importance. Here, we have synthesized three Fe-based polytantalotungstates, [Fe4(CH3COO)2(OH)5(H2O)9]2[Fe4(CH3COO)(OH)4(H2O)10(P2W12 Ta6O62)]2·166H2O (1), K4[Fe4(OH)2(H2O)14(P2W12Ta6O62)]2·72H2O (2), and K4H2[Fe4(HCOO)2(OH)(H2O)12(P2W12Ta6O62)]2·121H2O (3), using K11Li[P2W12(TaO2)6O56]·19H2O ({P2W12(TaO2)6}), [Fe3O(CH3COO)6(H2O)3]NO3·4H2O, and [Fe3O(O2CH)6(H2O)3]NO3. Enhanced basicity/nucleophilicity of Ta-bound oxygen atoms in {P2W12(TaO2)6} eliminates peroxo groups, enabling metal-ion incorporation. Catalyst 1 achieves quantitative THN oxidation (99%) through unprecedented Fe-ligand-POM cooperation, exhibiting broad visible absorption, tailored band positions, and prolonged charge separation. As the first robust heterogeneous system for aerobic THN photooxidation under an O2 atmosphere, it sets new standards for polyoxometalate photocatalyst design. However, the requirement of blue-light irradiation and limited substrate scope highlight areas for future optimization.
Phytochemical investigation of the n-butanol extracts of the herbaceous stems of Epheda intermedia led to the isolation of eight flavonoids that included three new flavonoid glycosides (1-3) and five previously reported analogues (4-8). Their structures have been identified on the basis of various spectral data. Besides, all the flavonoids were tested in vitro for their ability to inhibit α-glucosidase under the positive control of acarbose, and the results indicated that none of them exhibited significant inhibitory effect on α-glucosidase at 100 μM.
The heteropolyoxotantalates (hetero-POTas) represent a fascinating class of compounds characterized by diverse structural variations and outstanding physicochemical properties. However, the development of hetero-POTas remains an intriguing challenge due to factors such as the indigent solubility, the terribly sluggish reaction kinetics, and the high alkaline reaction atmosphere of the POTa category. In this study, the first hetero-POTa containing Si element, Li7KNa11H6[Si2Ta24(O2)20O52(OH)9]85H2O (1), was created through self-assembly in a neutral solution. The polyoxoanions embrace 5 tetrahedral {[Ta(O2)O5]4}, 4 {TaO6} and 1 {Si2O7} unit. The compound is the largest hetero-POTa at present. Additionally, 1 has a decent proton conductivity performance with proton conductivity of 3.63 x 10-3 S cm-1. Compound 1 is the first hetero-POTa containing Si element, and the largest hetero-POTa at present. The proton conductivity of 1 reaches 3.63 x 10-3 S cm-1 at 75 degrees C and 95% RH, which is comparable to the proton-conducting POMs reported.
Six undescribed compounds (1-6) and twenty-three known analogues (7-29) were isolated from the fresh roots of Rehmannia glutinosa. The structures of the compounds (1-29) were established through the application of spectroscopic analysis. Compounds 3, 4, 6, 8, 13, 18, 21, 22, 25, and 28 exhibited excellent anti-pulmonary fibrosis activity. The potential mechanistic pathway of 3 was also investigated, whose results indicate that compound 3 ameliorate TGF-(31 induced BEAS-2B cell injury via PI3K/AKT/NF-kappa B signaling pathway.
Two new undescribed compounds, jiofuran acid A (1) and 8′-hydroxyl episesaminone (2), together with seven known compounds (3–9) were isolated from the fresh roots of Zhongsheng No.1 Rehmannia glutinosa. Their structures were established by spectroscopic techniques (HR-ESI-MS, 1D NMR, 2D NMR), and absolute configurations were resolved by comparing their experimental and calculated ECD spectra. Bioassay results demonstrated compounds 1–3 exhibited the obvious anti-pulmonary fibrosis activity.
Photocatalytic carbon dioxide reduction is considered as an important stratege to solve environmental problem such as greenhouse gases, but designing and synthesizing effective photocatalysts is a challenge. In recent years,...
Ternary-component BiOBr/Bi/BiOI composites were successfully prepared by a one-step hydrothermal method under the reducing effect of ascorbic acid. Ascorbic acid not only converts Bi3+ to Bi-0 as a reducing agent, but also inhibits the growth of grains and controls the morphology, resulting in a multilayered hierarchical floral structure of the BiOBr/Bi/BiOI composites formed by the assembly of nanosheets dotted with nanoparticles on the surface. The composite has highest photocurrent density, lowest photogenerated electron-hole recombination rate and high specific surface area, and exhibits excellent degradation performance for both single and mixed pollutant systems of tetracycline, rhodamine B and methylene blue. h(+) is the most dominant reactive oxygen species in the photodegradation process, while center dot OH and center dot O-2(-) provide weak auxiliary degradation. A Z-scheme photocatalytic degradation mechanism of BiOBr/Bi/BiOI with excellent photocatalytic performance was proposed.
A 6-Ti-substituted polyoxometalate, (NH4)(5)Cs7Na3H2[Cs@(Ti2GeMo10O39)(3)]34H(2)O (1), was synthesized by reacting (NH4)(6)Mo7O244H(2)O, GeO2, and TiOSO4 through the conventional aqueous method. Polyanion 1a is composed of three {Ti2GeMo10} segments linked by Ti-O-Ti linkages and shows a trefoil-shaped structure. Furthermore, one Cs+ cation is encapsulated in the cavity of 1a. Notably, it possesses the highest number of Ti centers among the reported polyoxomolybdates. In addition, serving as a high-efficiency heterogeneous catalyst, 1 enables the conversion of methyl phenyl sulfide within 20 min, yielding 96.4% of the corresponding sulfoxide with good recyclability.
A chemical investigation of Anthriscus sylvestris roots led to the isolation and characterization of two new nitrogen-containing phenylpropanoids (1–2) and two new phenol glycosides (8–9), along with fifteen known analogues. Structure elucidation was based on HRESIMS, 1D and 2D NMR spectroscopy, and electronic circular dichroism (ECD). In addition, compounds 3, 6, 9–10, 12, and 17 exhibited inhibitory effects against the abnormal proliferation of pulmonary arterial smooth muscle cells with IC50 values ranging from 10.7 ± 0.6 to 57.1 ± 1.1 μM.
Two uncharacterized monoterpenoids (1-2) and six known analogues (3-8) were isolated from the fruit of Gardenia jasminoides. Their structures were determined by comprehensive spectroscopic data analysis, and the absolute configuration of 2 was elucidated by comparing the calculated electronic circular dichroism (ECD) spectrum with experimental ECD spectrum. Additionally, the results of preliminary activity evaluation indicated that these compounds showed slightly a-glucosidase inhibitory activity.
A heteropolytungstate cluster [{Ru2O(bpy)2}2{Bi2W32O110}]10- (bpy = C10H8N2) was incorporated into a 2 : 1 type layered porous framework by interweaving the Na+ bridged cluster chains through the hydrogen bonding ability of the bpy ligands. It features multiple pore channels rich in hydrogen-bond network, contributing high conductivities > 10-2 S cm-1 at 298-358 K and 85% RH.
A high-nuclearity carboxylic-modified heteropolyoxovanadate, Na2K10H15[P8VIV24(tart)15(H2O)15(OH)O51]·58H2O [1, tart = C4H2O6], has been successfully synthesized by a conventional aqueous method under mild conditions. The crystallographic study reveals that compound 1 crystallizes in the tetragonal I41/a space group and is composed by a trilayer saddle-like polyoxoanion {P8V24}. Two {V3(tart)(H2O)O11} as linking units bridge the top {P4VIV9(tart)7(H2O)4(OH)O23} and the bottom {P4VIV9(tart)6(H2O)9O22} layers via tartrate ligands and {PO4} tetrahedra, resulting in a 24-nuclearity POV skeleton structure. More interestingly, compound 1 serves as a heterogeneous catalyst for the selective oxidation of diphenylmethanes with 96.2% conversion and 93.6% selectivity under the optimized conditions.
Three pairs of undescribed diarylpentanoid enantiomers (1-3) and five undescribed phenylpropanoids (4-8), along with seven known compounds, were isolated from the roots of Anthriscus sylvestris. The structures of compounds (1-8) were determined by analysis of their 1D and 2D NMR spectra, HRESIMS, and electronic circular dichroism. In addition, the inhibitory activities against hypoxia-stimulated pulmonary arterial smooth muscle cells abnormal proliferation were evaluated by MTT assay. The mRNA expression levels of Bcl-2, BAX, Caspase3, and IL-6 were detected by quantitative real-time PCR. The results showed that compounds (-)-1, (+)-1, (-)-2, (+)-3, 4, 8-10, 14, and 15 inhibited the abnormal proliferation of PASMCs by regulating the levels of apoptosis and inflammatory factors.
Three isomorphic polytungstates, Cs9K18H10{[Sm2(H2O)4W4O10(AsW9O33)3]2(N(CH2PO3)2)}·46.5H2O (1), Cs10K9H18{[Eu2(H2O)4W4O10(AsW9O33)3]2(N(CH2PO3)2)}·41.5H2O (2), Cs10K9H18{[Gd2(H2O)4W4O10 (AsW9O33)3]2(N(CH2PO3)2)}·46H2O (3), have been successfully synthesized and characterized by routine methods, and demonstrated excellent catalytic activities in Knoevenagel condensation reaction as heterogeneous catalysts. Notably, catalyst 1 achieved higher reaction activity than catalysts 2 and 3, where a satisfactory reaction yield (95%) and high TON value (6380) could be obtained at moderate reaction condition. In addition, in the scale-up experiment, with the help of catalyst 1, 7.8 g benzaldehyde and 5.7 g ethyl cyanoacetate could transform into corresponding condensation product with a satisfactory yield (83%) and impressive TON value (13,883).
The oxidation of silanes into silanols is a very necessary transformation, and yet the rational fabrication of efficient catalysts for this reaction remains a challenging task. Here, a 3D polyoxometalate-based metal-organic framework (POMOF), [CuΙ3(pz)3{PMo12O40}]·H2O (HENU-8, HENU = Henan University; pz = pyrazine) was consciously prepared and first employed in the oxidation of dimethylphenylsilane with tert-butyl hydroperoxide (TBHP) as an oxidant, achieving 89% yield at a production rate of 132 mmol·g-1·h-1. Control experiments indicated that polyoxometalates and Cu atoms together affected the ultimate outcome in this catalytic system, and the designed catalyst followed a free radical mechanism.
Nine undescribed compounds, together with 21 known components, were isolated from the fresh roots of Rehmannia glutinosa. Their structures were elucidated based on spectroscopic data analysis, and the absolute configurations of undescribed compounds were determined by comparison of their calculated and experimental electronic circular dichroic (ECD) spectra and interpretation of their optical rotation data. The α-glucosidase inhibitory effects of the isolated compounds were investigated and all of them exhibited slightly inhibitory activities.