Abscisic acid-mediated cytosolic Ca2+ modulates triterpenoid accumulation of Ganoderma lucidum. / è„±è½é ¸ä»‹å¯¼èƒžå† Ca2+参与调控灵芝三萜积累.

Ganoderma lucidum is a mushroom widely used for its edible and medicinal properties. Primary bioactive constituents of G. lucidum are ganoderic triterpenoids (GTs), which exhibit important pharmacological activity. Abscisic acid (ABA), a plant hormone, is associated with plant growth, development, and stress responses. ABA can also affect the growth, metabolism, and physiological activities of different fungi and participates in the regulation of the tetracyclic triterpenes of some plants. Our findings indicated that ABA treatment promoted GT accumulation by regulating the gene expression levels (squalene synthase (sqs), 3-hydroxy-3-methylglutaryl-CoA reductase (hmgr), and lanosterol synthase (ls)), and also activated cytosolic Ca2+ channels. Furthermore, under ABA mediation, exogenous Ca2+ donors and inhibitors directly affected the cytosolic Ca2+ concentration and related gene expression in Ca2+ signaling. Our study also revealed that ABA-mediated cytosolic Ca2+ played a crucial regulatory role in GT biosynthesis, accompanied by antioxidant defense modulation with increasing superoxide dismutase (SOD) activity and ascorbate peroxidase (APX) activity, and the resistance ability of O2•- and glutathione (GSH) contents.

Heme oxygenase-1/carbon monoxide signaling participates in the accumulation of triterpenoids of Ganoderma lucidum.

Ganoderic triterpenoids (GTs) are the primary bioactive constituents of the Basidiomycotina fungus, Ganoderma lucidum. These compounds exhibit antitumor, anti-hyperlipidemic, and immune-modulatory pharmacological activities. This study focused on GT accumulation in mycelia of G. lucidum mediated by the heme oxygenase-1 (HO-1)/carbon monoxide (CO) signaling. Compared with the control, hemin (10 µmol/L) induced an increase of 60.1% in GT content and 57.1% in HO-1 activity. Moreover, carbon monoxide-releasing molecule-2 (CORM-2), CO donor, increased GT content by 56.0% and HO-1 activity by 18.1%. Zn protoporphyrin IX (ZnPPIX), a specific HO-1 inhibitor, significantly reduced GT content by 26.0% and HO-1 activity by 15.8%, while hemin supplementation reversed these effects. Transcriptome sequencing showed that HO-1/CO could function directly as a regulator involved in promoting GT accumulation by regulating gene expression in the mevalonate pathway, and modulating the reactive oxygen species (ROS) and Ca2+ pathways. The results of this study may help enhance large-scale GT production and support further exploration of GT metabolic networks and relevant signaling cross-talk.

2D Fe-doped NiO nanosheets with grain boundary defects for the advanced oxygen evolution reaction.

Two-dimensional (2D) nanomaterials with grain boundary defects are attractive to researchers in many fields, such as energy conversion and storage, sensing, catalysis and biological medicine. In this work, a nanostructure of 2D Fe-doped NiO nanosheets (NiFexO) with grain boundary defects was designed and applied in the electrocatalytic oxygen evolution reaction. This nanomaterial was synthesized through a solvothermal strategy followed by a thermally driven conversion process. In general, NiFexO electrocatalysts were fabricated with gradual morphological variation depending on the atomic ratio of Ni : Fe. It is surprising that the Fe content determines the electrocatalytic performance and the overpotential of water oxidation exhibits an inverted volcanic pattern. As expected, the as-prepared 2D NiFe0.1O nanosheets with grain boundary defects exhibit enhanced OER activity (274 mV@10 mA cm-2) compared with the oxide electrocatalyst reported in 1.0 M KOH owing to the advantages of abundant active sites. This work will shed light on the design and fabrication of novel-structured nanocatalysts.

A quencher-free 2-aminopurine modified hairpin aptasensor for ultrasensitive detection of Ochratoxin A.

A sensitive, efficient and quencher-free fluorescence aptasensor to detect Ochratoxin A (OTA) based on aptamer, 2-aminopurine (2AP) labeled Oligonucleotide sequence, as well as exonuclease I (Exo I) activity was developed. In which the aptamer specific to OTA was modified into a hairpin structure, and 8 bases at the 3' ends are exposed (H); also, 2AP is embedded in the oligonucleotide complementary to the 8 bases (2AP-probe).The detection principle based on 2AP-probe could be bonded to its complementary sequence and quenches the fluorescence of 2AP; The aptamer has a stronger affinity for the target than its complementary sequence; Exo I can dissociate single-stranded DNA and has little effect on double-stranded DNA as well as folded DNA. In the absence of OTA, the fluorescence of 2AP is quenched due to the complementary pairing of H and 2AP-probe; in the presence of OTA, H selective binding target is detached from 2AP-probe, and the fluorescence of 2AP is slightly restored. Moreover, when the Exo I is added to the detection system, 2AP-probe is dissociated by the Exo I to release the free 2AP, and the fluorescence of the system is further enhanced thereby realizing the detection of OTA. The detection limit of the aptasensor was low as 0.03 nM with a linear range of 0.5-100 nM. Moreover, the aptasensor has good selectivity and practicability and also has good potential in realizing the detection of toxic and harmful substances in food complex matrices.

An Interfacial Electron Transfer on Tetrahedral NiS2 /NiSe2 Heterocages with Dual-Phase Synergy for Efficiently Triggering the Oxygen Evolution Reaction.

Tetrahedral NiS2 /NiSe2 heterocages with rich-phase boundaries are synthesized through a simultaneous sulfuration/selenylation process using Ni-based acetate hydroxide prisms as precursor. Such a nanocage-like NiS2 /NiSe2 heterostructure can expose more active sites, accelerate the mass transport of the ions/gas, and optimize the interfacial electronic structure, which shows a significantly lower overpotential of 290 mV at 20 mA cm-2 than those of NiS/NiS2 and NiSe2 as counterparts. The experimental characterizations and theoretical density functional theory (DFT) calculations unveil that the interfacial electron transfer from NiSe2 to NiS2 at the heterointerface can modulate the electronic structure of NiS2 /NiSe2 , which further cooperates synergistically to change the Gibbs free energy of oxygen-containing intermediates as the rate-determining step (RDS) from 2.16 eV (NiSe2 ) and 2.10 eV (NiS2 ) to 1.86 eV (NiS2 /NiSe2 heterostructures) during the oxygen evolution reaction (OER) process. And as a result, tetrahedral NiS2 /NiSe2 heterocages with dual-phase synergy efficiently trigger the OER process, and accelerate the OER kinetics. This work provides insights into the roles of the interfacial electron transfer in electrocatalysis, and can be an admirable strategy to modulate the electronic structure for developing highly active electrocatalysts.

Alkaline-Etched NiMgAl Trimetallic Oxide-Supported KMoS-Based Catalysts for Boosting Higher Alcohol Selectivity in CO Hydrogenation.

The acidity/alkalinity and structural properties of NiMgAl trimetallic oxides (MMOs) can be effectively modulated by the alkaline-etching process with various etching times, which are further used as a support to prepare KMoS-based catalysts through the cetyltrimethylammonium bromide-encapsulated Mo-precursor strategy. The enriched surface anion groups in alkaline-etched MMO affect the textural properties, metal-support interaction, and sulfidation degree of the as-synthesized KMoS-based catalysts. As a result, KMoS-based catalysts using alkaline-etched MMO as supports effectively enhance the reducibility and dispersion of Mo species, which exert a positive influence on higher alcohol synthesis (HAS) performance in CO hydrogenation. A proper balance between acidity/alkalinity and structural properties in K, Mo/MMO- x catalysts can significantly enhance the alcohol selectivity in HAS from 55 to 65% (carbon selectivity). The formation of C2+ alcohols can be boosted by adol condensation with optimal acidic/basic properties via suppressing the acidity and increasing the amount of basic sites. The alkaline-etching process also significantly improves the space time yield of C2+ alcohols over unit mass of molybdenum.

Simultaneous Modulation of Composition and Oxygen Vacancies on Hierarchical ZnCo2 O4 /Co3 O4 /NC-CNT Mesoporous Dodecahedron for Enhanced Oxygen Evolution Reaction.

Electrochemical water splitting is a promising way for the sustainable production of hydrogen, but the efficiency of the overall water-splitting reaction largely depends on the oxygen evolution reaction (OER) because of its sluggish kinetics. Herein, a series of hierarchical ZnCo2 O4 /Co3 O4 /NC-CNT (NC-CNT=nitrogen-rich carbon nanotube) mesoporous dodecahedrons grafted to carbon nanotubes have been synthesized from ZnCo bimetallic zeolitic imidazolate frameworks (ZnCo-ZIFs) through sequential pyrolysis in nitrogen and mild oxidation in air. The simultaneous modulation of oxygen vacancies, composition, and hierarchical mesoporous architecture remarkably enhanced their electronic conduction and the amount and reactivity of accessible actives; thus boosting their intrinsic activity in the OER. The optimal ZnCo2 O4 /Co3 O4 /NC-CNT-700 sample exhibited a large current density of 50 mA cm-2 at a potential of 1.65 V, a small Tafel slope of 88.5 mV dec-1 , and superior stability in alkaline media. This work should provide a facile strategy for the rational design of advanced OER catalysts by simultaneous engineering of oxygen vacancies and composition.

Apoptosis induction of colorectal cancer cells HTL-9 in vitro by the transformed products of soybean isoflavones by Ganoderma lucidum.

Soybean isoflavones have been one of the potential preventive candidates for antitumor research in recent years. In this paper, we first studied the transformation of soybean isoflavones with the homogenized slurry of Ganoderma lucidum. The resultant transformed products (TSI) contained (703.21±4.35) mg/g of genistein, with transformed rates of 96.63% and 87.82% of daidzein and genistein, respectively, and TSI also could enrich the bioactive metabolites of G. lucidum. The antitumor effects of TSI on human colorectal cancer cell line HTL-9, human breast cancer cell line MCF-7, and human immortalized gastric epithelial cell line GES-1 were also studied. The 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2-H-tetrazolium bromide (MTT) assay showed that TSI could dramatically reduce the viability rates of HTL-9 cells and MCF-7 cells without detectable cytotoxicity on GES-1 normal cells when the TSI concentration was lower than 100 µg/ml. With 100 µg/ml of TSI, HTL-9 cells were arrested in the G1 phase, and late-apoptosis was primarily induced, accompanied with partial early-apoptosis. TSI could induce primarily early-apoptosis by arresting cells in the G1 phase of MCF-7 cells. For HTL-9 cells, Western-blot and reverse-transcriptase polymerase chain reaction (RT-PCR) analysis showed that TSI (100 µg/ml) can up-regulate the expression of Bax, Caspase-3, Caspase-8, and cytochrome c (Cyto-c), indicating that TSI could induce cell apoptosis mainly through the mitochondrial pathway. In addition, the expression of p53 was up-regulated, while the expression of Survivin and nuclear factor κB (NF-κB) was down-regulated. All these results showed that TSI could induce apoptosis of HTL-9 cells by the regulation of multiple apoptosis-related genes.

Submerged fermentation production and characterization of intracellular triterpenoids from Ganoderma lucidum using HPLC-ESI-MS.

As the main bioactive metabolites of Ganoderma lucidum, triterpenoids have various pharmacological effects. In this paper, the nutritional requirements and culture conditions of a submerged culture of G. lucidum were optimized using the response surface methodology; maximum mycelia biomass and intracellular triterpenoid production reached 1.87 g/100 ml and 93.21 mg/100 ml, respectively, for a culture consisting of wort 4.10% (0.041 g/ml) and yeast extract 1.89% (0.0189 g/ml), pH 5.40. For the first time, we established that wort, which is cheap and abundant, can replace the more commonly used glucose as the sole source of carbohydrate. Using high-performance liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS), 10 major ganoderic acids were tentatively identified based on the predominant fragmentation pathways with the elimination of H2O and CO2, as well as cleavage of the D-ring.