Novel Alkaloids from Aspergillus fumigatus VDL36, an Endophytic Fungus Associated with Vaccinium dunalianum.

Eleven alkaloids (1-11) including seven new ones, 1-7, were isolated from the solid fermentation of Aspergillus fumigatus VDL36, an endophytic fungus isolated from the leaves of Vaccinium dunalianum Wight (Ericaceae), a perennial evergreen shrub distributed across the Southwest regions of China, Myanmar, and Vietnam. Their structures were elucidated on the basis of extensive spectroscopic methods. The isolates were evaluated for in vitro antifungal activities against five phytopathogenic fungi (Fusarium oxysporum, Coriolus versicolor, Fusarium solani, Botrytis cinerea, Fusarium graminearum). As a result, the new compounds fumigaclavine I (1), 13-ethoxycyclotryprostatin A (5), 13-dehydroxycyclotryprostatin A (6), and 12ß-hydroxy-13-oxofumitremorgin C (7) exhibited antifungal activities with MIC values of 7.8-62.5 µg/mL which were comparable to the two positive controls ketoconazole (MIC = 7.8-31.25 µg/mL) and carbendazim (MIC = 1.95-7.8 µg/mL). Furthermore, compounds 1 and 5 demonstrated potent protective and curative effects against the tomato gray mold in vivo. Preliminary structure-activity relationships of the tested indole diketopiperazine alkaloids indicate that the introduction of a substituent group at position C-13 enhances their biological activities.

Hydrogen-rich syngas upgrading via CO2 adsorption by amine-functionalized Cu-BTC: the effect of different amines.

Syngas produced from supercritical water gasification typically contain a high amount of CO2 along with H2. In order to improve the quality of syngas, amine-functionalized copper benzene-1,3,5-tricarboxylate (Cu-BTC) was synthesized as an effective adsorbent for selective removal of CO2 from syngas to increase the concentration of H2. The amines used in this study included monoethanolamine (MEA), ethylenediamine (EDA), and polyethyleneimine (PEI). The fundamental physicochemical character of adsorbents, CO2 adsorption capacity, and CO2/H2 selectivity were analyzed. The physicochemical characterization indicated that the structure of amine-functionalized Cu-BTC was partially damaged, which resulted in a decrease in specific surface area and pore volume. On the other hand, the enlarged pore size was beneficial for the mass transfer of gas in the adsorbent. Among these adsorbents, Cu-BTC/PEI exhibited the maximum CO2 adsorption capacity of 3.83 mmol/g and the highest CO2/H2 selectivity of 19.74. It was found that the adsorption pressure is the most significant factor for the CO2 adsorption capacity. Lower temperature and higher pressure were favored for CO2 adsorption capacity and CO2/H2 selectivity, so physical adsorption by Cu-BTC played a dominant role. Moreover, Cu-BTC/PEI can be well-regenerated with stable adsorption efficiency after five consecutive cycles. These findings suggested that Cu-BTC/PEI could be a promising alternative adsorbent for CO2 capture from syngas.

Toonanoronoids A-E, five new limonoids from Toona ciliata var. yunnanensis.

Five new B-seco-limonoids, namely toonanoronoids A-E (1-5), in conjunction with three previously reported compounds, were isolated from the EtOAc extract of the twigs and leaves of Toona ciliata var. yunnanensis. Their structures were elucidated through comprehensive spectroscopic and X-ray crystallographic analysis. The cytotoxic activities of new compounds against five human tumor cell lines (HL-60, SMMC-7721, A549, MCF-7, and SW480) were screened, Compounds 4 and 5 exerted inhibition toward two tumor cell lines (HL-60, SW-480) with IC50 values between 1.7 and 5.9 µM.

6'-O-Caffeoylarbutin from Quezui Tea: A Highly Effective and Safe Tyrosinase Inhibitor.

Tyrosinase is vital in fruit and vegetable browning and melanin synthesis, crucial for food preservation and pharmaceuticals. We investigated 6'-O-caffeoylarbutin's inhibition, safety, and preservation on tyrosinase. Using HPLC, we analyzed its effect on mushroom tyrosinase and confirmed reversible competitive inhibition. UV_vis and fluorescence spectroscopy revealed a stable complex formation with specific binding, causing enzyme conformational changes. Molecular docking and simulations highlighted strong binding, enabled by hydrogen bonds and hydrophobic interactions. Cellular tests showed growth reduction of A375 cells with mild HaCaT cell toxicity, indicating favorable safety. Animal experiments demonstrated slight toxicity within safe doses. Preservation trials on apple juice showcased 6'-O-caffeoylarbutin's potential in reducing browning. In essence, this study reveals intricate mechanisms and applications of 6'-O-caffeoylarbutin as an effective tyrosinase inhibitor, emphasizing its importance in food preservation and pharmaceuticals. Our research enhances understanding in this field, laying a solid foundation for future exploration.

Comparative Analysis of the Wood Metabolites of Three Poplar Clones Using UPLC-Triple-TOF-MS.

Poplar, a woody tree species, is widely used for industrial production and as a protective forest belt. Different clones of poplar exhibit clear variation in terms of morphological and physiological features, however, the impact of the genetic variation on the composition and abundance of wood metabolite have not been fully determined. In this study, ultra-high pressure liquid chromatography-triple time of flight-mass spectrometer (UPLC-Triple-TOF-MS) was used to explore the metabolite changes in poplar wood from three clones, including Populus deltoides CL. '55/65', P. deltoides CL. 'Danhong', and P. nigra CL. 'N179'. A total of 699 metabolites were identified. Clustering analysis and principal component analysis display that the metabolic differences of wood have allowed distinguishing different species of poplar. Meanwhile, eight significantly different metabolites were screened between P. deltoides and P. nigra, which may be considered as valuable markers for chemotaxonomy. In addition, the highly discriminant 352 metabolites were obtained among the three clones, and those may be closely related to the distinction in unique properties (e.g., growth, rigidity and tolerance) of the poplar wood cultivars. This study provides a foundation for further studies on wood metabolomics in poplar, and offers chemotaxonomic markers that will stimulate the early screening of potentially superior trees.

A novel "turn on" fluorescence probe based on a caffeic acid skeleton for detecting Al3+ and bioimaging application.

The specificity detection of Al3+ is important for monitoring life health and environmental pollution. A fluorescence enhancement probe based on caffeic acid HAM was synthesized for detecting Al3+ with high sensitivity and good selectivity. When Al3+ was added in the aqueous solution of HAM, the formation of HAM-Al3+ complexes inhibited the PET process, which led to great enhancement of fluorescence. The addition of other metal ions cannot induce the change of fluorescence intensity. The sensing mechanism was proved by 1H NMR titration, MS, and Job's plot. Moreover, probe HAM exhibited excellent properties, such as high sensitivity (LOD = 0.168 µM), fast response time (30 s), wide pH range (3-11), and good interference ability. Based on the above results, probe HAM was used to explore its bioimaging application in biological samples.

Subcritical Water Extraction of Phenolic Compounds from Vaccinium Dunalianum Wight Leaves and Their Antioxidant and Tyrosinase Inhibitory Activities in Vitro.

Subcritical water extraction was used to extract bioactive phenolic compounds from Vaccinium dunalianum Wight leaves. The optimal extraction conditions were determined as an extraction temperature of 150 °C, an extraction time of 40 min, and a liquid-solid ratio of 35 : 1 mL/g. The total phenolic content reached 21.35 mg gallic acid /g, which was 16 % higher than that by hot water extraction. The subcritical water extraction extract exhibited strong scavenging activity of DPPH free radical and ABTS+ free radical, as well as significant tyrosinase inhibitory activity. The study suggests that subcritical water extraction can alter the composition of the extracts, leading to the production of various phenolic compounds, effective antioxidants, and tyrosinase inhibitors from Vaccinium dulciana Wight leaves. These findings confirm the potential of Vaccinium dunalianum Wight as a natural antioxidant molecule source for the medicine and food industries, and for the therapy of skin pigmentation disorders.

An integrated transcriptomic and metabolomic analysis for changes in rose plant induced by rose powdery mildew and exogenous salicylic acid.

We explored the transcriptomic and metabolomic changes in Rosa chinensis after the infection with Podosphaera pannosa and after the treatment with exogenous salicylic acid (SA), separately. The rose responses to the mildew-infection were clearly similar to the responses to the SA-treatment. Based on the combined omics analysis, after the induction by both P. pannosa and SA, R. chinensis responded consistently by MAPK cascades, plant-pathogen interaction pathway activation, and resistance (R) genes expression, and further, triterpenoid biosynthesis, glutathione metabolism, and linoleic acid metabolism were significantly enriched when compared with the control. The levels of the triterpenoids with the largest fold change values were significantly up-regulated such as dehydro (11,12) ursolic acid lactone and maslinic acid, suggesting that these pathways and metabolites were involved in the resistance to P. pannosa. The contents of salicylic acid beta-D-glucoside, methyl salicylate, and methyl jasmonate increased significantly resulting from both P. pannosa-infection and exogenous SA-treatment.

C21, C22 pregnane glycosides and cytotoxic C27 spriostanol steroids from Asparagus cochinchinesis.

A preliminary chemical investigation on 70% MeOH extract of the roots of Asparagus cochinchinensis resulted in the isolation of nine steroids. These isolates comprised of four new C21 (1-4) and one new pregnane (5) glycosides, and four known C27 (6-9) spirostanol steroids. Their structures were identified via analysis of the spectroscopic data and the results of hydrolytic cleavage. The cytotoxic activities of the compounds were tested toward the human tumor cell line Hela (cervical cancer), and compounds 7 and 8 displayed moderate activity with IC50 values of 35.5 and 39.6 µM, respectively.

Matched Field Processing Based on Bayesian Estimation.

In order to improve the robustness and positioning accuracy of the matched field processing (MFP) in underwater acoustic systems, we propose a conditional probability constraint matched field processing (MFP-CPC) algorithm in this paper, which protects the main-lobe and suppresses the side-lobe to the AMFP by the constraint parameters, such as the posterior probability density of source locations obtained by Bayesian criterion under the assumption of white Gaussian noise. Under such constraint, the proposed MFP-CPC algorithm not only has the same merit of a high resolution as AMFP but also improves the robustness. To evaluate the algorithm, the simulated and experimental data in an uncertain shallow ocean environment is used. From the results, MFP-CPC is robust to the moored source, as well as the moving source. In addition, the localization and tracking performances of using the proposed algorithm are consistent with the trajectory of the moving source.

Cytotoxic Limonoids from the Twigs and Leaves of Toona ciliata.

Eight new limonoids, toononoids A-H (1-8), eight new B-seco-29-norlimonoids, toonanoronoids A-H (9-16), and seven known analogues were obtained from the EtOAc extract of the twigs and leaves of Toona ciliata. Compounds 2, 4, 8, and 16 are rare lactam-bearing limonoids. Compounds 1, 14, and 15 possess an unusual γ-methoxybutenolide moiety at C-17, while compounds 9, 10, and 15 have a rare 3ß-hydroxy group. Their 2D structure and relative configurations were identified using spectroscopic data. The absolute configurations of 1, 9, 14, and 15 were established via X-ray diffraction crystallography or comparison of experimental and calculated ECD data. The cytotoxicity of the compounds was assessed toward five human tumor cell lines, and their anti-inflammatory activity was assessed based on NO production using LPS-stimulated RAW264.7 macrophages. Compounds 11 and 12 exerted inhibition toward two tumor cell lines (MCF-7, SW-480) with IC50 values between 2.1 and 3.7 µM, while 18-22 inhibited the proliferation of HL-60, MCF-7, and SW-480 cells (IC50 0.6-4.0 µM). Only compound 4 exhibited weak anti-inflammatory activity with an IC50 value of 28.3 µM.

Cytotoxicity of Triterpenoid Alkaloids from Buxus microphylla against Human Tumor Cell Lines.

Three new triterpenoid alkaloids, namely buxmicrophyllines P-R (1-3), were isolated from the twigs and leaves of Buxus microphylla. Their structures were elucidated on the basis of NMR and MS spectroscopic analyses. Structurally, compounds 1-3 belong to the 9,10-cycloartane type alkaloids. In addition, compound 3 exhibited moderate cytotoxic activities in vitro against HL-60, SMMC-7221, A-549, MCF-7, and SW480 cell lines (with IC50 values ranging from 4.51 to 15.58 µM).

Six New 9,19-Cycloartane Triterpenoids from Cimicifuga foetida L.

Six new 9,19-cycloartane triterpene derivatives, as well as 3 known analogues (7-9), were isolated from the roots of Cimicifuga foetida L. Their structures were established on the basis of extensive spectroscopic analyses (IR, UV, ORD, HRESIMS, 1D and 2D NMR).

Pepluane and Paraliane Diterpenoids from Euphorbia peplus with Potential Anti-inflammatory Activity.

Twelve new diterpenoids based on two rare skeletal types, namely, paralianones A-D (1-4) and pepluanols A-H (5-12), along with five known compounds, were isolated from an acetone extract of Euphorbia peplus. Their structures were proposed based on 1D and 2D NMR spectroscopic data analysis. These diterpenoids were evaluated for potential anti-inflammatory activity in a lipopolysaccharide-stimulated mouse macrophage cellular model. Compounds 3, 4, 11, 13, and 16 displayed moderate inhibitory effects on NO inhibition, with IC50 values ranging from 29.9 to 38.3 µM.

Antioxidant farnesylated hydroquinones from Ganoderma capense.

Phytochemical investigation of the fruiting bodies of Ganoderma capense led to isolation of eight aromatic meroterpenoids (1-8). Ganocapensins A and B (1, 2) possessed a thirteen-membered and a fourteen-membered ether rings, respectively. The structures of new isolates including absolute configuration were elucidated on the basis of extensive spectroscopic technologies and Mosher's method. All isolated compounds showed significant antioxidant effects with IC50 values ranging from 6.00±0.11 to 8.20±0.30µg/ml in the DPPH radical scavenging assay.

One-Step Semisynthesis of a Segetane Diterpenoid from a Jatrophane Precursor via a Diels-Alder Reaction.

A novel segetane diterpenoid (1) and four jatrophane diterpenoids (2-5) were isolated from an acetone extract of Euphorbia peplus. Due to quantity limitations, we prepared 1 via a Diels-Alder reaction, an approach motivated by this compound's biosynthetic pathway and successfully performed X-ray analysis of 1. Furthermore, in an in vitro activity test, 1 exhibited moderate anti-inflammatory activity, whereas both its precursor (2) and the relevant intermediate (2a, IC50 = 1.56 µM) exhibited significant anti-inflammatory activity.

Matched Field Processing Based on Least Squares with a Small Aperture Hydrophone Array.

The receiver hydrophone array is the signal front-end and plays an important role in matched field processing, which usually covers the whole water column from the sea surface to the bottom. Such a large aperture array is very difficult to realize. To solve this problem, an approach called matched field processing based on least squares with a small aperture hydrophone array is proposed, which decomposes the received acoustic fields into depth function matrix and amplitudes of the normal modes at the beginning. Then all the mode amplitudes are estimated using the least squares in the sense of minimum norm, and the amplitudes estimated are used to recalculate the received acoustic fields of the small aperture array, which means the recalculated ones contain more environmental information. In the end, lots of numerical experiments with three small aperture arrays are processed in the classical shallow water, and the performance of matched field passive localization is evaluated. The results show that the proposed method can make the recalculated fields contain more acoustic information of the source, and the performance of matched field passive localization with small aperture array is improved, so the proposed algorithm is proved to be effective.

Cycloartane Glycosides from the Roots of Cimicifuga foetida with Wnt Signaling Pathway Inhibitory Activity.

Four new 9,19-cycloartane triterpenoids, cimilactone E (1), cimilactone F (2), 2'-O-(E)-butenoyl-23-epi-26-deoxyactein (3), and 2',12ß-O-diacetylcimiracemonol-3-O-ß-d-xylopyranoside (4), together with four known constituents (5-8) were isolated from the roots of Cimicifuga foetida. The new structures were elucidated by extensive spectroscopic analysis. In addition, compounds 7 and 8 showed significant Wnt signaling pathway inhibitory activity, with IC50 values of 3.33 and 13.34 µM, respectively, using the luciferase reporter gene assay.

Cytotoxic 9,19-cycloartane triterpenes from the aerial parts of Cimicifuga yunnanensis.

Six new 9,19-cycloartane triterpenes (1-6) were isolated from the aerial parts of Cimicifuga yunnanensis. The new chemical structures were determined by extensive analyses of 1D and 2D NMR spectroscopy. Compounds 1 and 2 are the first 9,19-cycloartane triterpenes characterized by CH3-18 shifting from C-13 to C-12 in the Cimicifuga spp. The evaluation of inhibition activity against human HL-60, SMMC-7721, A-549, MCF-7, and SW480 cell lines indicated that compounds 1-6 showed different levels of cytotoxic activities with IC50 values ranging from 1.2 to 27.8 µm.

Steroidal saponins from the roots of Asparagus cochinchinensis.

AIM: To study the chemical constituents of the roots of Asparagus cochinchinensis (Asparagaceae). METHODS: The compounds were isolated with Diaion HP20, silica gel, and ODS chromatography, and their structures were determined on the basis of chemical methods, HR-ESI-MS, and 1D- and 2D-NMR techniques. RESULTS: Seven compounds were isolated from the n-butanol fraction of the roots of A. cochinchinensis, and their structures were elucidated as (25S)-26-O-ß-D-glucopyranosyl-5ß-furostan-3ß, 22α, 26-triol-12-one-3-O-ß-D-glucopyranoside (1), (25S)-26-O-ß-D-glucopyranosyl-22α-methoxy-5ß-furostan-3ß, 26-diol-12-one-3-O-ß-D-glucopyranoside (2), (25S)-26-O-ß-D-glucopyranosyl-5ß-furostan-3ß, 22α, 26-triol (3), (25S)-26-O-ß-D-glucopyranosyl-5ß-furstan-3ß, 22α, 26-triol-3-O-ß-D-glucopyranoside (4), (25S)-26-O-ß-D-glucopyranosyl-5ß-furostan-3ß, 22α, 26-triol-3-O-α-L-rhamnopyranosyl-(1, 4)-ß-D-glucopyranoside (5), (25S)-5ß-spirostan-3ß-ol-3-O-α-L-rhamnopyranoside (6), and (25S)-5ß-spirostan-3ß-ol-3-O-ß-D-glucopyranoside (7). CONCLUSION: Compounds 1 and 2 were two new furostanol saponins.