Dimensionally Intact Construction of Ultrathin S-Scheme CuFe2O4/ZnIn2S4 Heterojunctional Photocatalysts for CO2 Photoreduction.

The conversion of CO2 into carbon-neutral fuels such as methane (CH4) through selective photoreduction is highly sought after yet remains challenging due to the slow multistep proton-electron transfer processes and the formation of various C1 intermediates. This research highlights the cooperative interaction between Fe3+ and Cu2+ ions transitioning to Fe2+ and Cu+ ions, enhancing the photocatalytic conversion of CO2 to methane. We introduce an S-scheme heterojunction photocatalyst, CuFe2O4/ZnIn2S4, which demonstrates significant efficiency in CO2 methanation under light irradiation. The CuFe2O4/ZnIn2S4 heterojunction forms an internal electric field that aids in the mobility and separation of exciton carriers under a wide solar spectrum for exceptional photocatalytic performance. Remarkably, the optimal CuFe2O4/ZnIn2S4 heterojunction system achieved an approximately 68-time increase in CO2 conversion compared with ZnIn2S4 and CuFe2O4 nanoparticles using only pure water, with nearly complete CO selectivity and yields of CH4 and CO reaching 172.5 and 202.4 µmol g-1 h-1, respectively, via a 2-electron oxygen reduction reaction (ORR) process. The optimally designed CuFe2O4/ZnIn2S4 heterojunctional system achieved approximately 96% conversion of BA and 98.5% selectivity toward benzaldehyde (BAD). Additionally, this photocatalytic system demonstrated excellent cyclic stability and practical applicability. The photogenerated electrons in the CuFe2O4 conduction band enhance the reduction of Fe3+/Cu2+ to Fe2+/Cu+, creating a microenvironment conducive to CO2 reduction to CO and CH4. Simultaneously, the appearance of holes in the ZnIn2S4 valence band facilitates water oxidation to O2. The synergistic function within the CuFe2O4/ZnIn2S4 heterojunction plays a pivotal role in facilitating charge transfer, accelerating water oxidation, and thereby enhancing CO2 reduction kinetics. This study offers valuable insights and a strategic framework for designing efficient S-scheme heterojunctions aimed at achieving carbon neutrality through solar fuel production.

A Comparative Analysis of Chemical Constituents and Antioxidant Effects of Dendrobium fimbriatum Hook Fractions with Different Polarities.

The aim of this study was to investigate the chemical composition and antioxidant capacity of various polar fractions obtained from Dendrobium fimbriatum Hook (DH). First, a 90% ethanol-aqueous extract of DH (CF) was subjected to sequential fractionation using different organic solvents, resulting in the isolation of a methylene chloride fraction (DF), an ethyl acetate fraction (EF), an n-butanol fraction (BF), and a remaining water fraction (WF) after condensation. Additionally, the CF was also subjected to column chromatography via a D101 macroreticular resin column, eluted with ethanol-aqueous solution to yield six fractions (0%, 20%, 40%, 60%, 80%, and 100%). UPLC-Q-Exactive Orbitrap-MS/MS analysis identified a total of 47 chemical compounds from these polar fractions, including fatty acids, amino acids, phenolic acids, flavonoids, organic heterocyclic molecules, and aromatic compounds. Moreover, DF, EF, and the 60%, 80%, and 100% ethanol-aqueous fractions had higher total phenol content (TPC) and total flavonoid content (TFC) values and greater 2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS-) and 1,1-diphenyl-2-picrylhydrazyl (DPPH)-scavenging abilities. In H2O2-induced HepG2 cells, the aforementioned fractions could increase the activities of antioxidative enzymes NAD(P)H: quinone oxidoreductase 1 (NQO1), superoxide dismutase (SOD), heme oxygenase-1 (HO-1) and catalase (CAT), stimulate glutathione (GSH) synthesis by increasing the activities of glutamic acid cysteine ligase (GCL) and glutathione synthetase (GS), regulate GSH metabolism by increasing glutathione peroxidase (GSH-Px) and glutathione reductase (GR) activities, and reduce levels of reactive oxygen species (ROS) and malondialdehyde (MDA). Furthermore, the antioxidative stress effect of the DH fractions was found to be positively correlated with the activation of nuclear factor-erythroid 2-related factor 2 (Nrf2) protein and the presence of antioxidative chemical constituents. In conclusion, this study highlights the efficacy of both liquid-liquid extraction and macroporous resin purification techniques in the enrichment of bioactive compounds from natural food resources. The comprehensive analysis of chemical constituents and antioxidant effects of different polar fractions from Dendrobium fimbriatum Hook contributes to the understanding of its potential application in functional foods and nutraceuticals.

Anti-leukemic effect and molecular mechanism of 11-methoxytabersonine from Melodinus cochinchinensis via network pharmacology, ROS-mediated mitochondrial dysfunction and PI3K/Akt signaling pathway.

Melodinus cochinchinensis (Lour.) Merr. is a Yunnan endemic folk medicine. Our previous study showed that 11-methoxytabersonine (11-MT) isolated from M. cochinchinensis has strong cytotoxicity on human T-ALL cells, but its molecular mechanism has not been studied. In current study, the cytotoxicity and possible mechanism of 11-MT on T-cell acute lymphoblastic leukemia was explored using network pharmacology and molecular biology techniques. 11-MT significantly inhibited the cell proliferations on different four human T-ALL cells (MOLT-4, Jurkat, CCRF-CEM, and CEM/C1 cells). 11-MT triggered ROS accumulation, calcium concentration and cell apoptosis, and decreased the mitochondrial membrane potential (MMP) in human T-ALL cells, especially MOLT-4 cells. Western blot analysis showed that it can induce MOLT-4 cell apoptosis by up-regulating PI3K/Akt signaling pathway. Therefore, 11-MT induces human T-ALL cells apoptosis via up-regulation of ROS-mediated mitochondrial dysfunction and down-regulation of PI3K/Akt/mTOR signaling pathway.

Involucrasin C, Anti-Inflammatory 2,3-Dihydro-1H-Indene Derivative from Chinese Dai Ethnic Medicine Shuteria involucrata.

(±)-Involucrasin C (1), a pair of new 2,3-dihydro-1H-indene enantiomers, along with an enantiomeric analog (2), were isolated from Shuteria involucrata. Their structures were established by the basis of comprehensive spectroscopic data analysis and X-ray crystallographic diffraction. Both 1 and 2 significantly inhibited the secretion of pro-inflammatory cytokines IL-6, TNF-α, and IL-1ß, suggesting that these two natural 2,3-dihydro-1H-indene derivatives may be active components of S. involucrata and may block inflammation in the initial stage.

(±)-Involucrasins A and B, two pairs of flavanone enantiomers from Shuteria involucrata and their inhibitory effects on the proliferation of various cancer cell lines.

(±)-Involucrasins A (1) and B (2), two pairs of flavanone enantiomers were isolated from Shuteria involucrata. Structurally, both 1 and 2 are rare representatives of 5-dehydroxy/5-demethoxy 2',3',4'-trisubstituted flavanones. Their structures were elucidated on the basis of comprehensive spectroscopic data analysis and comparison with the literature data. Involucrasin B (2) exhibited moderate anti-proliferative activity against Caco-2, MCF-7, MDA-MB-468, and HCT116 cell lines with IC50 values ranging from 7.9-22.7 µM. Involucrasin A (1) exhibited weak inhibitory activity against Caco-2 and MCF-7 cell lines with IC50 values of 25.8 and 26.5 µM, respectively.

Impacts of pyrolysis temperatures on physicochemical and structural properties of green waste derived biochars for adsorption of potentially toxic elements.

This study comparatively investigated the influence of changes in pyrolysis temperature on the physicochemical, structural, and adsorptive properties of biochars derived from a green waste (Cynodon dactylon L.). For this purpose, the biophysically dried green wastes were pyrolyzed at 400 °C, 600 °C, and 800 °C under the same pyrolysis conditions. The results revealed that the physicochemical and structural properties were varied, depending upon the pyrolysis temperatures. With the increase of pyrolysis temperature, the surface functional groups were escaped, the structure became more porous (pore volume of 0.089 ± 0.001), the metal oxides were remained consistent, and the biochars turned into more alkaline nature (pH of 11.9 ± 0.2). Furthermore, as referring to the adsorptive performance for potentially toxic elements, with experimental adsorption capacity of up to 33.7 mg g-1 and removal rate up to 96% for a multi-metals containing solution, the biochars pyrolyzed at high temperature (800 °C) was significantly (p < 0.05) higher than those pyrolyzed at low temperature (400 °C). According to the physicochemical and structural properties, and the adsorptive performances of the biochars, the optimal pyrolysis temperature was herein recommended to be 800 °C.

Hepatoprotective Polysaccharides from Geranium wilfordii: Purification, Structural Characterization, and Their Mechanism.

Traditional Chinese Medicine is generally used as a decoction to guard health. Many active ingredients in the decoction are chemical ingredients that are not usually paid attention to in phytochemical research, such as polysaccharides, etc. Based on research interest in Chinese herbal decoction, crude polysaccharides from G. wilfordii (GCP) were purified to obtain two relatively homogeneous polysaccharides, a neutral polysaccharide (GNP), and an acid polysaccharide (GAP) by various chromatographic separation methods, which were initially characterized by GC-MS, NMR, IR, and methylation analysis. Studies on the hepatoprotective activity of GCP in vivo showed that GCP might be a potential agent for the prevention and treatment of acute liver injury by inhibiting the secretion levels of ALT, AST, IL-6, IL-1ß, TNF-α, and MDA expression levels, increasing SOD, and the GSH-Px activity value. Further, in vitro assays, GNP and GAP, decrease the inflammatory response by inhibiting the secretion of IL-6 and TNF-α, involved in the STAT1/T-bet signaling pathway.

Cu(II)-Catalyzed C-N, C-O, C-Cl, C-S, and C-Se Bond Formation via C(sp2)-H Activation Using 7-Azaindole as an Intrinsic Directing Group.

A general protocol has been developed for the construction of carbon-heteroatom (C-N, C-Cl, C-O, C-S, and C-Se) bonds using the bench stable, earth-abundant, and environmentally benign copper catalyst. Only oxygen is sufficient to regenerate the copper catalyst. Control experiments suggested that the proto-demetalation step is reversible. Depending on the coupling partner, the reaction follows either disproportionation or radical pathways to complete the catalytic cycle. The synthetic utility of the developed protocol has been demonstrated via various functional group transformations.

Diastereoselective [3 + 2] Cycloaddition of Quinoxalin-2(1H)-ones with Donor-Acceptor Cyclopropanes: Efficient Synthesis of Tetrahydro pyrrolo[1,2-a]quinoxalin-4(5H)-ones.

A ytterbium triflate-catalyzed diastereoselective [3 + 2] cycloaddition of quinoxalinones with donor-acceptor cyclopropanes and cyclobutanes is described. A series of tetrahydropyrrolo-quinoxalinone derivatives were obtained in high yields (up to 96%) with excellent diastereoselectivities (up to 46:1). Other medicinally important heterocycles like benzoxazinone, isoquinoxalinone, and dibenzoxazepine derivatives were also suitable for the desired annulation reaction. The current method is applicable for the scale-up reaction. Further, the utility of this annulation reaction is demonstrated by the synthesis of densely functionalized proline derivatives.

Polymethylated acylphloroglucinols from Rhodomyrtus tomentosa exert acetylcholinesterase inhibitory effects.

Chemical investigation of the twigs and leaves of Rhodomyrtus tomentosa led to the isolation and structural identification of a novel polymethylated phloroglucinol meroterpenoid (PPM) featuring a 6/6/6/6 tetracyclic system, rhotomentodione F (1), five new polymethylated polycyclic phloroglucinols (PPPs) with a rare bis-furan framework, rhotomentosones A-E (2-6), and one new adduct composed of an acylphloroglucinol and two ß-triketone units, rhotomentosone F (7), as well as five known analogues (8-12). Their structures and absolute configurations were unambiguously determined by comprehensive spectroscopic data and electronic circular dichroism (ECD) calculations. All isolates were evaluated for their anti-inflammatory and acetylcholinesterase (AChE) inhibitory activities. Compound 6 displayed significant AChE inhibitory effect with an IC50 value of 8.68 µM. Further molecular docking studies of 6 revealed that the interactions with AChE residues Ser125, Glu202, and Tyr133 are crucial for AChE inhibitory activity. The current study not only enriches the chemical diversity of phloroglucinols in Myrtaceae species, but also provides potential lead compounds for the further design and development of new AChE inhibitors to treat Alzheimer's disease.

The Bioavailability, Extraction, Biosynthesis and Distribution of Natural Dihydrochalcone: Phloridzin.

Phloridzin is an important phytochemical which was first isolated from the bark of apple trees. It is a member of the dihydrochalcones and mainly distributed in the plants of the Malus genus, therefore, the extraction method of phloridzin was similar to those of other phenolic substances. High-speed countercurrent chromatography (HSCCC), resin adsorption technology and preparative high-performance liquid chromatography (HPLC) were used to separate and purify phloridzin. Many studies showed that phloridzin had multiple pharmacological effects, such as antidiabetic, anti-inflammatory, antihyperglycaemic, anticancer and antibacterial activities. Besides, the physiological activities of phloridzin are cardioprotective, neuroprotective, hepatoprotective, immunomodulatory, antiobesity, antioxidant and so on. The present review summarizes the biosynthesis, distribution, extraction and bioavailability of the natural compound phloridzin and discusses its applications in food and medicine.

Activity Guided Isolation of Phenolic Compositions from Anneslea fragrans Wall. and Their Cytoprotective Effect against Hydrogen Peroxide Induced Oxidative Stress in HepG2 Cells.

Anneslea fragrans Wall., commonly known as "Pangpo Tea", is traditionally used as a folk medicine and healthy tea for the treatment of liver and intestine diseases. The aim of this study was to purify the antioxidative and cytoprotective polyphenols from A. fragrans leaves. After fractionation with polar and nonpolar organic solvents, the fractions of aqueous ethanol extract were evaluated for their total phenolic (TPC) and flavonoid contents (TFC) and antioxidant activities (DPPH, ABTS, and FRAP assays). The n-butanol fraction (BF) showed the highest TPC and TFC with the strongest antioxidant activity. The bio-guided chromatography of BF led to the purification of six flavonoids (1-6) and one benzoquinolethanoid (7). The structures of these compounds were determined by NMR and MS techniques. Compound 6 had the strongest antioxidant capacity, which was followed by 5 and 2. The protective effect of the isolated compounds on hydrogen peroxide (H2O2)-induced oxidative stress in HepG2 cells revealed that the compounds 5 and 6 exhibited better protective effects by inhibiting ROS productions, having no significant difference with vitamin C (p > 0.05), whereas 6 showed the best anti-apoptosis activity. The results suggest that A. fragrans could serve as a valuable antioxidant phytochemical source for developing functional food and health nutraceutical products.

Bioactivity-Guided Isolation of Phytochemicals from Vaccinium dunalianum Wight and Their Antioxidant and Enzyme Inhibitory Activities.

Vaccinium dunalianum Wight, usually processed as a traditional folk tea beverage, is widely distributed in the southwest of China. The present study aimed to investigate the antioxidant, α-glucosidase and pancreatic lipase inhibitory activities of V.dunalianum extract and isolate the bioactive components. In this study, the crude extract (CE) from the buds of V. dunalianum was prepared by the ultrasound-assisted extraction method in 70% methanol and then purified with macroporous resin D101 to obtain the purified extract (PM). Five fractions (Fr. A-E) were further obtained by MPLC column (RP-C18). Bioactivity assays revealed that Fr. B with 40% methanol and Fr. D with 80% methanol had better antioxidant with 0.48 ± 0.03 and 0.62 ± 0.01 nM Trolox equivalent (TE)/mg extract for DPPH, 0.87 ± 0.02 and 1.58 ± 0.02 nM TE/mg extract for FRAP, 14.42 ± 0.41 and 19.25 ± 0.23 nM TE/mg extract for ABTS, and enzyme inhibitory effects with IC50 values of 95.21 ± 2.21 and 74.55 ± 3.85 for α-glucosidase, and 142.53 ± 11.45 and 128.76 ± 13.85 µg/mL for pancreatic lipase. Multivariate analysis indicated that the TPC and TFC were positively related to the antioxidant activities. Further phytochemical purification led to the isolation of ten compounds (1-10). 6-O-Caffeoylarbutin (7) showed significant inhibitory effects on α-glucosidase and pancreatic lipase enzymes with values of 38.38 ± 1.84 and 97.56 ± 7.53 µg/mL, and had the highest antioxidant capacity compared to the other compounds.

Penipyranicins A-C: Antibacterial Methylpyran Polyketides from a Hydrothermal Spring Sediment Penicillium sp.

Four new aromatic polyketides (1-4) were isolated from Penicillium sp. RO-11, obtained from the sediment of a hydrothermal spring in the southwestern region of Saudi Arabia. The new compounds are penipyranicins A-C (1-3), characterized by a 4-methyl-4H-pyran moiety, a structural motif unprecedented among fungal polyketides, and the naphthopyrone derivative isopyrenulin (4). The structures of the new compounds were elucidated on the basis of data from mass spectrometry, 1D and 2D NMR analysis, and comparison between experimental and time-dependent density functional theory-calculated electronic circular dichroism spectra. A plausible biosynthetic pathway connecting penipyranicins and isopyrenulin is proposed. The isolated compounds were active against Gram-positive and Gram-negative bacteria.

Antibacterial and Antifungal Sesquiterpenoids from Aerial Parts of Anvillea garcinii.

Two new sesquiterpenoids belonging to the guaiane, 4α,9α,10α-trihydroxyguaia-11(13)en-12,6α-olide (1), and germacrane, 9ß-hydroxyparthenolide-9-O-ß-D-glucopyranoside (2), classes have been isolated from the leaves of the Saudi medicinal plant Anvillea garcinii along with seven known compounds (3-9). The structures of the new metabolites were elucidated by spectroscopic analysis, including one-dimensional (1D) and two-dimensional (2D) Nuclear Magnetic Resonance (NMR) and high-resolution electrospray ionization mass spectrometry (HR-ESIMS). The antimicrobial properties of 1-9 were screened against seven different pathogenic microbes, and compounds 1-3 showed a potent antifungal activity.

Cu(II)-Mediated Cross-Dehydrogenative Coupling of Indolines with Sulfonamides, Carboxamides, and Amines.

A facile and efficient Cu-mediated protocol for the cross-dehydrogenative coupling of indoline with sulfonamides, carboxamides, and anilines is reported. The reaction takes place through Cu-mediated C7-H activation via a 6-membered metallacycle to afford the amide and amine derivatives in good yields with a wide range of functional group tolerance. The importance of the protocol has been demonstrated by synthesizing the antiproliferative agent, ER-67836.

Unprecedented sugar bridged bisindoles selective inhibiting glioma stem cells.

Unlike reported bisindoles linked by single bond directly, alstoniasidines A (1) and B (2), from Alstonia scholaris featuring unprecedented skeleton with two indole moieties bridged by a sugar, represented a novel bisindole type having strictosamide-glucopyranose-picraline scaffold. Both compounds exhibited selective cytotoxicity against human glioma stem cells (GSCs) and induced caspase-3 dependent extrinsic apoptosis by increasing the expression of interleukin 1 (IL-1), tumor necrosis factor (TNF-α), and the cleaved caspase-3, while damaged the unlimited proliferation and self-renewal capacity of GSCs. This finding might provide new type of leads for the selective killing of human glioma stem cells.

Eucalypglobulusals A-J, Formyl-Phloroglucinol-Terpene Meroterpenoids from Eucalyptus globulus Fruits.

Ten new formyl-phloroglucinol-terpene meroterpenoids, eucalypglobulusals A-J (1-10), and ten known analogues were isolated from  Eucalyptus globulus fruits. The structures of 1-10 were determined by spectroscopic analysis, while their absolute configurations were established using calculated and experimental electronic circular dichroism (ECD) spectra. Eucalypglobulusal A was assigned as a new formyl-phloroglucinol-terpene meroterpenoid with a rearranged sesquiterpene skeleton, and an aldol condensation between C-3 and C-5 of the germacrene C moiety was proposed to be a key step in its putative biosynthetic pathway. Eucalypglobulusal F exhibited cytotoxicity against the human acute lymphoblastic cell line (CCRF-CEM) with an IC50 value of 3.3 µM, while eucalypglobulusal A, eucarobustol C, macrocarpal A, macrocarpal B, and macrocarpal D exhibited DNA topoisomerase I (Top1) inhibition. The compounds eucalypglobulusal A and macrocarpal A act as Top1 catalytic inhibitors and delay Top1 poison-mediated DNA double-strand damage.

Evaluation of antioxidant and antimicrobial activities of Bergenia ciliata Sternb (Rhizome) crude extract and fractions.

Biologically, screening of medicinal plants extracts have been since pre-historic to determine the antioxidants and antimicrobial profile. The present study was aimed to investigate and evaluate crude extract and different fractions of Bergenia ciliata Sternb (rhizome) for bioactivity which is most considerable medicinal plants. The chloroform fraction was found to be highly anti-oxidative with the IC50 value (4.15±0.82) as compare to ethyl acetate and n-hexane fraction. In addition, neither crude extract nor any fraction showed inhibition against fungal strains, i.e. Aspergillus flavus and Aspergillus niger. Furthermore, the crude extract and fractions of B. ciliata (rhizome) exhibiting promising activities against Bacillus atrophoeus, Bacillus subtilis, Kleibsiella pneumonia and Pseudomonas aeruginosa strains. In summary, B. ciliata is recommended as a source of bioactive compounds which might be used against oxidative stress and drug resistance bacteria.

Sweritranslactones A-C: Unusual Skeleton Secoiridoid Dimers via [4 + 2] Cycloaddition from Swertiamarin.

Skeleton-diversity-oriented chemical conversion from pure natural products is a valuable method to obtain natural product-like compounds, especially those with novel architecture. The application of phytochemical methods to iridoids yielded three novel secoiridoid dimers: sweritranslactones A-C (1-3). These molecules possess a 6/6/6/6/6/6-fused hexacyclic skeleton and were obtained from swertiamarin, one of the major constituents of the genus Swertia, via a [4 + 2] cycloaddition and intramolecular nucleophilic addition under aqueous conditions. The structures were established based on extensive spectroscopic characterization and X-ray crystallographic diffraction analysis.