海南石斛化学成分研究

为了解海南石斛(Dendrobium hainanense Rolfe)的化学成分,采用色谱技术从海南石斛茎叶中分离得到14个化合物,经波谱分析分别鉴定为:2,6-二甲氧基对苯醌(1)、(+)-dehydrovomifoliol(2)、blumenol A(3)、2,7-二羟基-3,4-二甲氧基-9,10-二氢菲(4)、2,7-二羟基-3,4-二甲氧基菲(5)、3,7-二羟基-2,4-二甲氧基菲(6)、3-羟基-2,4,7-三甲氧基-9,10-二氢菲(7)、3-羟基-2,4,7-三甲氧基菲(8)、3,4,7-三羟基-2-甲氧基菲(9)、3,7-二羟基-2,4-二甲氧基-9,10-二氢菲(10)、(+)-lyoniresinol(11)、丁香脂素(12)、denchrysan A(13)和nobilone(14)。这些化合物均为首次从海南石斛中分离得到。活性测试结果表明化合物4~6、8~9、11和14对乙酰胆碱酯酶有抑制活性。     

Isolation and identification of potent allelopathic substances in rattail fescue

Aqueous methanol extracts of rattail fescue (Vulpia myuros) inhibited the growth of roots and shoots of cress (Lepidium sativum), lettuce (Lactuca sativa), alfalfa (Medicago sativa), timothy (Phleum pratense), Digitaria sanguinalis and Lolium multiflorum. Increasing the extract concentration increased the inhibition, suggesting that rattail fescue may have growth inhibitory substances and possess allelopathic potential. The aqueous methanol extract of rattail fescue was purified and two main inhibitory substances were isolated and identified by spectral data as (−)-3-hydroxy-β-ionone and (+)-3-oxo-α-ionol. Both substances inhibited root and shoot growth of cress at concentrations greater than 0.3 μM. The concentrations required for 50% growth inhibition on root and shoot growth of cress, lettuce, alfalfa, timothy, D. sanguinalis and L. multiflorum were 2.7–19.7 μM for (−)-3-hydroxy-β-ionone, and 2.1–34.5 μM for (+)-3-oxo-α-ionol. The concentration of (−)-3-hydroxy-β-ionone and (+)-3-oxo-α-ionol, respectively, in rattail fescue was 7.8 and 3.7 μg g⁻¹ fresh weight. Considering the endogenous level and the inhibitory activity, (−)-3-hydroxy-β-ionone and (+)-3-oxo-α-ionol may work as allelopathic substances in rattail fescue through the growth inhibition of neighboring plant species.     

Tyrosinase inhibitory activities of the compounds isolated from Neolitsea aciculata (Blume) Koidz.

This study was designed to investigate the mushroom tyrosinase inhibitory activity for the constituents isolated from Neolitsea aciculata. The stems of N. aciculata was extracted with aqueous ethanol and subjected to chromatographic separation, which led to the isolation of 11 compounds: methyl linoleate (1), catechin (2), epicatechin (3), afzelin-7-O-glucopyranoside (4), 2′,3′-di-(p-coumaroyl)afzelin (5), 2′-p-coumaroylafzelin (6), feruloyl tyramine (7), β-sitosterol (8), daucosterol (9), oleic acid (10), and trilaurin (11). Their structures were elucidated on the basis of spectroscopic studies as well as by comparison with the data available in the literature. Among these isolates, compounds 5 and 6 were identified as potent mushroom tyrosinase inhibitors with IC₅₀ values of 0.067 and 0.080 mM, respectively. The inhibition kinetics, analysed by Lineweaver–Burk plots, indicated that compounds 5 and 6 are competitive tyrosinase inhibitors when using l-tyrosine as a substrate. Notably, compounds 1–11 were isolated for the first time from this plant. These results provide evidence that this plant might be a potential source of anti-melanogenesis agents.     

Synthesis,characterization, cytotoxicity,and DNA binding of some new platinum(II) and platinum(IV) complexes with benzimidazole ligands

In this study, two Pt(II) and three Pt(IV) complexes with the structures of [PtL₂Cl₂] (1), [PtL₂I₂] (2), [PtL₂Cl₂(OH)₂] (3), [PtL₂Cl₂(OCOCH₃)₂] (4), and [PtL₂Cl₄] (5) (L = benzimidazole as carrier ligand) were synthesized and evaluated for their in vitro antiproliferative activities against the human MCF-7, HeLa, and HEp-2 cancer cell lines. The influence of compounds 1–5 on the tertiary structure of DNA was determined by their ability to modify the electrophoretic mobility of the form I and II bands of pBR322 plasmid DNA. The inhibition of BamH1 restriction enzyme activity of compounds 1–5 was also determined. In general, it was found that compounds 1–5 were less active than cisplatin and carboplatin against MCF-7 and HeLa cell lines (except for 1, which was found to be more active than carboplatin against the MCF-7 cell line). Compounds 1 and 3 were found to be significantly more active than cisplatin and carboplatin against the HEp-2 cell line.     

Allelopathic potential of Bothriochloa laguroides var. laguroides (DC.) Herter (Poaceae: Andropogoneae)

Bothriochloa laguroides var. laguroides (DC.) Herter, a native bluestem of America, has been shown to produce many biologically active compounds. The allelopathic potential of aqueous extracts from roots, stems and leaves was examined. Lettuce seeds (Lactuca sativa) and maize (Zea mays), the common allelopathy bioassay systems, as well as seeds from two native species, wintergreen paspalum (Paspalum guenoarum) and lovegrass (Eragrostis curvula), were germinated in the presence of aqueous extracts. Percent seed germination, root and shoot elongation were measured. After 4 and 7 days root, stem and leaf extracts caused inhibition of root and shoot elongation in all four species tested. Aqueous extracts were generally less inhibitory to seed germination. Aqueous extracts from different parts of B. laguroides var. laguroides show therefore allelopathic effects inhibiting, in particular, growth of competing plants.     

Synthesis of 4-(2-substituted hydrazinyl)benzenesulfonamides and their carbonic anhydrase inhibitory effects

In this study, 4-(2-substituted hydrazinyl)benzenesulfonamides were synthesized by microwave irradiation and their chemical structures were confirmed by ¹H NMR, ¹³CNMR, and HRMS. Ketones used were: Acetophenone (S1), 4-methylacetophenone (S2), 4-chloroacetophenone (S3), 4-fluoroacetophenone (S4), 4-bromoacetophenone (S5), 4-methoxyacetophenone (S6), 4-nitroacetophenone (S7), 2-acetylthiophene (S8), 2-acetylfuran (S9), 1-indanone (S10), 2-indanone (S11). The compounds S9, S10 and S11 were reported for the first time, while S1–S8 was synthesized by different method than literature reported using microwave irradiation method instead of conventional heating in this study. The inhibitory effects of 4-(2-substituted hydrazinyl)benzenesulfonamide derivatives (S1–S11) against hCA I and II were studied. Cytosolic hCA I and II isoenzymes were potently inhibited by new synthesized sulphonamide derivatives with K_is in the range of 1.79?±?0.22–2.73?±?0.08?nM against hCA I and in the range of 1.72?±?0.58–11.64?±?5.21?nM against hCA II, respectively.     

Kushenol A and 8-prenylkaempferol,tyrosinase inhibitors,derived from Sophora flavescens

Tyrosinase is known for an enzyme that plays a key role in producing the initial precursor of melanin biosynthesis. Inhibition of the catalytic reaction of this enzyme led to some advantage such as skin-whitening and anti-insect agents. To find a natural compound with inhibitory activity towards tyrosinase, the five flavonoids of kushenol A (1), 8-prenylkaempferol (2), kushenol C (3), formononetin (4) and 8-prenylnaringenin (5) were isolated by column chromatography from a 95% methanol extract of Sophora flavescens. The ability of these flavonoids to block the conversion of L-tyrosine to L-DOPA by tyrosinase was tested in vitro. Compounds 1 and 2 exhibited potent inhibitory activity, with IC50 values less than 10?µM. Furthermore, enzyme kinetics and molecular docking analysis revealed the formation of a binary encounter complex between compounds 1–4 and the enzyme. Also, all of the isolated compounds (1–5) were confirmed to possess antioxidant activity.     

Allelochemicals released by rice roots and residues in soil

A few rice (Oryza sativa L.) varieties or rice straw produce and release allelochemicals into soil in which interfere with the growth of neighboring or successive plants. Allelopathic rice PI312777 and Huagan-1 at their early growth stages released momilactone B, 3-isopropyl-5-acetoxycyclohexene-2-one-1, and 5,7,4′-trihydroxy-3′,5′-dimethoxyflavone into soil at phytotoxic levels, but non-allelopathic rice Huajingxian did not. Both allelopathic and non-allelopathic rice residues released momilactone B and lignin-related phenolic acids (p-hydroxybenzoic, p-coumaric, ferulic, syringic and vanillic acids) into the soil during residue decomposition to inhibit successive plants. The results indicated that allelochemicals involved in rice allelopathy from living and dead plants are substantially different. Interestingly, the concentrations of the allelochemicals released from the allelopathic rice seedlings in soil increased dramatically when they were surrounded with Echinochloa crus-galli. The concentrations of the allelochemicals were over 3-fold higher in the presence of E. crus-galli than in the absence of E. crus-galli. However, the same case did not occur in non-allelopathic Huajingxian seedlings surrounded with E. crus-galli. In addition to allelochemical exudation being promoted by the presence of E. crus-galli, allelopathic rice seedlings also increased allelochemical exudation in response to exudates of germinated E. crus-galli seeds or lepidimoide, an uronic acid derivative exuded from E. crus-galli seeds. These results imply that allelopathic rice seedlings can sense certain allelochemicals released by E. crus-galli into the soil, and respond by increased production of allelochemicals inhibitory to E. crus-galli. This study suggests that rice residues of both allelopathic and non-allelopathic varieties release similar concentrations and types of allelochemicals to inhibit successive plants. In contrast, living rice plants of certain allelopathic varieties appear to be able to detect the presence of interspecific neighbors and respond by increased allelochemicals.     

Identification of flavonolignans from Silybum marianum seeds as allosteric protein tyrosine phosphatase 1B inhibitors

Protein tyrosine phosphatase 1B (PTP1B) is an attractive molecular target for anti-diabetes, anti-obesity, and anti-cancer drug development. From the seeds of Silybum marianum, nine flavonolignans, namely, silybins A, B (1, 2), isosilybins A, B (3, 4), silychristins A, B (5, 6), isosilychristin A (7), dehydrosilychristin A (8), and silydianin (11) were identified as a novel class of natural PTP1B inhibitors (IC₅₀ 1.3 7–23.87?µM). Analysis of structure–activity relationship suggested that the absolute configurations at C-7" and C-8" greatly affected the PTP1B inhibitory activity. Compounds 1–5 were demonstrated to be non-competitive inhibitors of PTP1B based on kinetic analyses. Molecular docking simulations resulted that 1–5 docked into the allosteric site, including α3, α6, and α7 helix of PTP1B. At a concentration inhibiting PTP1B completely, compounds 1–5 moderately inhibited VHR and SHP-2, and weakly inhibited TCPTP and SHP-1. These results suggested the potentiality of these PTP1B inhibitors as lead compounds for further drug developments.     

ALLELOPATHIC MECHANISMS OF VELVETLEAF (ABUTILON THEOPHRASTI MEDIC., MALVACEAE) ON SOYBEAN

Sampling in a soybean field established that presence of velvetleaf (A. theophrasti) weeds interfered with soybean production. Number of soybean pods and number of pods/stem were significantly lower in transect segments adjacent to velvetleaf plants. In bioassays for phytotoxicity of velvetleaf, several dilutions of aqueous extracts from fresh field-collected leaves depressed germination of radish seeds and inhibited growth of soybean seedlings. Seed germination bioassays from eluates of chromatograms developed in one dimension showed that two of three bands containing phenolic compounds were inhibitory to radish seed germination. Soybeans inhibited by aqueous velvetleaf extracts had increased diffusive resistance, suggesting partial stomatal closure. Inhibited plants also gave evidence of water stress, with leaf water potentials often as low as –20 bars and reduced water content, when compared with controls. Quantification of chlorophyll on a leaf area basis showed that chlorophyll of inhibited plants was below controls. These data demonstrate the allelopathic potential of velvetleaf and suggest that interference with water balance and chlorophyll content may be two mechanisms of inhibitory action of toxins present in the leaves of velvetleaf.     

Rubralactone,Rubralides A,B and C,and Rubramin Produced by Penicillium rubrum

Rubralactone (1), rubralides A, B and C (2–4), rubramin (5), and 2-formyl-3,5-dihydroxy-4-methylbenzoic acid (6), were isolated from Penicillium rubrum, and their structures established by spectroscopic methods including 2D NMR. The effects on plant growth of 1–6 were examined using the lettuce seedling bioassay. Compound 1 promoted root growth. Compounds 2, 3 and 5 inhibited the growth of lettuce seedlings, but 4 and 6 did not have any inhibitory effect on their growth.     

Study of the antioxidant activity of Thymus sibthorpii Bentham (Lamiaceae)

Abstract

From the aerial parts of Thymus sibthorpii Bentham (Lamiaceae), five flavonoids apigenin (1), 7-methoxy-apigenin (2), naringenin (3), eriodictyol (4) and eriodictyol-7-glucoside (5), have been isolated together with caffeic acid methyl ester (6), rosmarinic acid (7) and rosmarinic acid methyl ester (8). The structures of the isolated compounds were established by spectroscopic methods. The extracts and the isolated compounds were tested for their free radical scavenging activity using the following in vitro assays: (i) interaction with the free stable radical of DPPH (1,1-diphenyl-2-picrylhydrazyl), (ii) inhibition of linoleic acid lipid peroxidation induced by the dihydrochloric acid of 2,2-azobis-2-amidinepropane (AAPH) and (iii) the scavenging activity of enzymatically produced superoxide anion. Their inhibitory activity toward soybean lipoxygenase was evaluated in vitro, using linoleic acid as a substrate. The antioxidant results of the extracts are discussed in terms of their constitution in phenolic compounds, which were determined following the Folin–Ciocalteu method.     

Effects of Seselin and Coumarin on Growth, Indoleacetic Acid Oxidase, and Peroxidase, with Special Reference to Cucumber (Cucumis sativa L.) Radicles

Seselin, a natural coumarin derivative isolated from citrus roots, inhibited radicle growth in seedlings of cucumber (Cucumis sativa), lettuce (Lactuca sativum), radish (Raphanus sativus), and wheat (Triticum aestivum) grown in the dark. Coumarin similarly inhibited radicle growth of cucumber seedlings. Growth retardation of the cucumber radicles was accompanied by an increased activity of peroxidase and indole-3-acetic acid oxidase. Both compounds antagonized indole-3-acetic acid-induced growth of wheat coleoptiles, whereas coumarin was much less effective than seselin in antagonizing gibberellic acid-induced release of reducing sugars from barley endosperm. It is suggested that seselin plays an important role in the regulation of root growth, and that it is the indole-3-acetic acid oxidase cofactor previously detected in citrus roots.     

Allelopathic influence of Vigna mungo (black gram) seeds on germination and radical growth of some crop plants

Intercropping of Vigna mungo (black gram) isprevalent for varied crop regimes in subtropical northern plains of India. Insugarcane, the negative impacts of a black gram intercrop on crop yields,rhizosphere soil properties and benefit: cost ratio have been reported. Thepossible allelopathic potential of black gram seeds on the germination,seedlingemergence and root elongation of other commercial crops is reported here. Theeffects of imbibed seeds of black gram, their aqueous leachate and seedextractson the germination and root elongation of seeds of four test crops viz. wheat,maize, gram and lentil, both under aseptic and soil conditions, wereinvestigated. Inhibitory effects were evident in all the bioassays of seeds ofthese crops. The black gram seeds directly and leachates were highly inhibitorybut the aqueous seed extract was less so. The observations indicate a releaseofinhibitory substances from black gram seeds leading to the observed inhibitoryeffects.     

Inhibitory effects on mushroom tyrosinase by flavones from the stem barks of Morus lhou (S.) Koidz

Five flavones displaying tyrosinase inhibitory activity were isolated from the stem barks of Morus lhou (S.) Koidz., a cultivated edible plant. The isolated compounds were identified as mormin (1), cyclomorusin (2), morusin (3), kuwanon C (4), and norartocarpetin (5). Mormin (1) was characterized as a new flavone possesing a 3-hydroxymethyl-2-butenyl at C-3. The inhibitory potencies of these flavonoids toward monophenolase activity of mushroom tyrosinase were investigated. The IC₅₀ values of compounds 1–5 for monophenolase activity were determined to be 0.088, 0.092, 0.250, 0.135 mM, and 1.2 μM, respectively. Mormin (1), cyclomorusin (2), kuwanon C (4) and norartocarpetin (5) exhibited competitive inhibition characteristics. Interestingly norartocarpetin (5) showed a time–dependent inhibition against oxidation of l–tyrosine: it also operated under the enzyme isomerization model (k₅ = 0.8424 min^{? 1}, k₆ = 0.0576 min^{? 1}, = 1.354 μM).     

Inhibition of soluble epoxide hydrolase activity by compounds isolated from the aerial parts of Glycosmis stenocarpa

The aim of this study is to search for soluble epoxide hydrolase (sEH) inhibitors from natural plants, bioassay-guided fractionation of lipophilic n-hexane and chloroform layers of an extract of the aerial parts of Glycosmis stenocarpa led to the isolation of 12 compounds (1–12) including murrayafoline-A (1), isomahanine (2), bisisomahanine (3), saropeptate (4), (24?S)-ergost-4-en-3,6-dione (5), stigmasta-4-en-3,6-dion (6), stigmast-4-en-3-one (7), β-sitosterol (8), 24-methylpollinastanol (9), trans-phytol (10), neosarmentol III (11) and (+)-epiloliolide (12). Their structures were elucidated on the basis of spectroscopic data. Among them, neosarmentol III (11) was isolated from nature for the first time. All the isolated compounds were evaluated for their inhibitory activity against sEH. Among isolated carbazole-type compounds, isomahanine (2) and bisisomahanine (3) were identified as a potent inhibitor of sEH, with IC₅₀ values of 22.5?±?1.7 and 7.7?±?1.2?µM, respectively. Moreover, the inhibitory action of 2 and 3 represented mixed-type enzyme inhibition.     

The impact of LED illumination on antioxidant properties of sprouted seeds

The objective of this study was to evaluate the effect of the light emitting diode (LED) spectra on the antioxidant properties of sprouted wheat (Triticum aestivum L.), radish (Raphanus sativus L.), and lentil (Lens esculenta Moenh.) seeds. Lighting experiments were performed under controlled conditions (PPFD - 100 μmol m⁻² s⁻¹; 12 h photoperiod; 27°C). The LED conditions used were: L1 - 638 nm; L2 - 455 nm, 638 nm, 669 nm, 731 nm (basal components); L3 - basal + 385 nm; L4 - basal + 510 nm and L5 - basal + 595 nm. Wheat and lentil sprouts were shown to accumulate less phenolic compounds and were more sensitive to light spectral differences when compared to radish sprouts. The antioxidant properties and contents of antioxidant compounds in seeds germinated in the dark were significantly lower than LED treated seeds. The higher content of total phenols and significant increase in alpha-tocopherol and vitamin C concentration resulted in altered DPPH free-radical scavenging capacity. Therefore we conclude that the LED spectra, based on basal components supplemented with green (510 nm) light can improve the antioxidant properties of sprouted seeds of lentil and wheat. The highest antioxidant properties of radish seeds were caused by radiation with supplemental amber (595 nm) light.     

牛至挥发油的化学成分及其化感作用

为探究牛至挥发油的化学成分及其化感作用,本文采用水蒸气蒸馏法提取牛至全草挥发油,利用气相色谱(GC)和气相色谱-质谱联用(GC-MS)从牛至挥发油中鉴定出14种化学成分,占总出峰面积的93.6%,主要成分为甲基丁香酚(16.5%)、肉豆蔻醚(15.6%)、香芹酚(15.0%)、百里香酚(9.8%)、洋芹脑(9.4%)等。通过测定挥发油对小麦、绿豆和萝卜种子萌发及幼苗生长的影响,评价挥发油的化感潜力。结果表明: 牛至挥发油对3种受体植物的种子萌发有抑制作用,其中,对小麦的抑制作用最强,萝卜和绿豆次之,挥发油对供试植物地上部分生长的抑制作用大于地下部分。挥发油对3种供试植物幼茎及小麦和萝卜幼根生长的抑制作用与浓度成正相关,对绿豆幼根长度则表现为“低促高抑”现象。本研究证实牛至挥发油中含有化感物质,其活性化合物及作用机制有待进一步研究。     

Insect Antifeedants,Pterocarpans and Pterocarpol,in Heartwood of Pterocarpus macrocarpus Kruz.

The insect antifeedant activities of pterocarpans and a sesquiterpene alcohol from the dichloromethane extract of Pterocarpus macrocarpus Kruz. (Leguminosae) were evaluated against the common cutworm, Spodoptera litura F. (Noctuidae), and the subterranean termite, Reticulitermes speratus (Kolbe)(Rhinotermitidae). Three pterocarpans, (?)-homopterocarpin (1), (?)-pterocarpin (2), and (?)-hydroxyhomopterocarpin (3) and the sesquiterpene alcohol, (+)-pterocarpol (5), were isolated from the dichloromethane extract of the heartwood of P. macrocarpus under guidance by a biological assay. Among these natural products, the most active insect antifeedant against both S. litura and R. speratus was 1. On the other hand, sesquiterpene alcohol 5 showed less insect antifeedant activity than the other pterocarpans against both insect species. While its methylated derivative, (?)-methoxyhomopterocarpin (4), showed high biological activity, 3 showed less insect antifeedant activity in this study. Interestingly, racemic 1 did not show insect antifeedant activity against S. litura. However, all of the test pterocarpans and isoflavones showed antifeedant activity against the test termites. Additionally, since these compounds were major constituents of P. macrocarpus, these antifeedant phenolics may act as chemical defense factors in this tree. In Thailand, lumber made from this tree is used to make furniture and in building construction due to its resistance to termite attack.     

Furanofuran lignans from Vitex negundo seeds

A new furanofuran lignan, vitelignin A (1), together with eight known lignan derivatives, were isolated from the seeds of Vitex negundo. Their structures were identified as (+)-4-oxo-8-hydroxy-2,6-di(3,4-methylenedioxy)phenyl-3,7-dioxabicyclo[3.3.0]octane (1), 4-oxosesamin (2), (+)-sesamin (3), (+)-paulownin (4), 4-hydroxysesamin (5), 4,8-dihydroxysesamin (6), 4-oxopaulownin (7), (+)-2-(3-methoxy-4-hydroxyphenyl)-6-(3,4-methylenedioxy)phenyl-3,7-dioxabicyclo[3.3.0]octane (8), and (+)-pinoresinol (9), respectively, based on extensive NMR and MS spectroscopic studies. Compounds 1, 2, and 7 showed moderate antifungal activity in vitro.