Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Keisuke Nishikawa , Hiroshi Fukuda , Masato Abe , Kazunari Nakanishi , Tomoya Taniguchi , Takashi Nomura , Chihiro Yamaguchi , Syuntaro Hiradate , Yoshiharu Fujii , Katsuhiro Okuda , Mitsuru Shindo 1-O-cis-Cinnamoyl-?-d-glucopyranose is one of the most potent allelochemicals that has been isolated from Spiraea thunbergii Sieb by Hiradate et al. It derives its strong inhibitory activity from cis-cinnamic acid (cis-CA), which is crucial for phytotoxicity. By preparing and assaying a series of cis-CA analogues, it was previously found that the key features of cis-CA for lettuce root growth inhibition are a phenyl ring, cis-configuration of the alkene moiety, and carboxylic acid. On the basis of a structure–activity relationship study, the substituent effects on the aromatic ring of cis-CA were examined by systematic synthesis and the lettuce root growth inhibition assay of a series of cis-CA analogues having substituents on the aromatic ring. While ortho- and para-substituted analogues exhibited low potency in most cases, meta-substitution was not critical for potency, and analogues having a hydrophobic and sterically small substituent were more likely to be potent. Finally, several cis-CA analogues were found to be more potent root growth inhibitors than cis-CA.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Xiang-Rong Cheng , Shou-De Zhang , Chun-Hui Wang , Jie Ren , Jiang-Jiang Qin , Xue Tang , Yun-Heng Shen , Shi-Kai Yan , Hui-Zi Jin , Wei-Dong Zhang Phytochemical investigation of Inula wissmanniana Hand.-Mazz. afforded 21 eudesmane and germacrane derivatives, including rare 4,5-secoeudesman-12,5-olide, eudesman-12,5-olide, 3,4-secoeudesman-12-oic acid, and germacra-4-en-12,6-olides. Their structures were elucidated by combinative analyses of MS, NMR, electronic circular dichroism, and X-ray crystallography data. Moreover, most of the isolates exhibited inhibition against lipopolysaccharide-induced nitric oxide production in RAW264.7 macrophages and cytotoxicity in HepG2, PC-3, and MGC-803 tumor cells.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Denise Brentan Silva , Laura Tiemi Okano , Norberto P. Lopes , Dionéia C.R. de Oliveira LC–DAD–MS/MS analysis of the Brazilian medicinal plant Bidens gardneri Bak. (Asteraceae) results in identification of eleven phenolic compounds. HRESIMS, MS/MS and UV data analyses, with phytochemicals isolation guided by MS data, results in flavanones?(?)-4?-methoxy-7-O-?-d-glucopyranosyl-8,3?-dihydroxyflavanone; (?)-7-O-(6?-E-p-coumaroyl)-?-d-glucopyranosyl-8,3?,4?-trihydroxyflavanone; and (?)-4?-methoxy-7-O-(6?-acetyl)-?-d-glucopyranosyl-8,3?-dihydroxyflavanone being identified-together with four known compounds. The absolute configurations of two of the flavanones were determined as 2S via circular dichroism.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Yoshinori Saito , Mayu Ichihara , Koji Takiguchi , Yui Tanio , Yasuko Okamoto , Ryo Hanai , Chiaki Kuroda , Takayuki Kawahara , Xun Gong , Motoo Tori Chemical constituents and evolutionally neutral DNA sequences of six samples of Cremanthodium lineare Maxim., collected in the Sichuan Province of China, were studied. Three samples produced furanoeremophilanes and the other three, eremophilan-8-ones. The chemotypes were found to be correlated with DNA sequence types, suggesting that the chemical diversity observed has a genetic origin. Production of furanoeremophilanes by a Cremanthodium species suggests an evolutionary relationship between Cremanthodium and Ligularia species, and possibly to related genera.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Antonia María Rojano-Delgado , Feliciano Priego-Capote , Francisco Barro , María Dolores Luque de Castro , Rafael De Prado The resistance to glufosinate of two lines—genetically modified (GM) and unmodified (T-590 and T-549, respectively)—of Triticum aestivum has been studied. In the GM line, the bar gene was introduced to increase the resistance to glufosinate. Experiments in a controlled growth chamber showed that line T-590 presented a high resistance to glufosinate with an ED50 value of 478.59g active ingredient per hectare (gaiha?1) versus 32.65gaiha?1 for line T-549. The activity of glutamine synthetase (GS) in leaf extracts from both lines was investigated. The I50 for line T-590 was 694.10?M glufosinate versus 55.46?M for line T-549, with a resistance factor of 12.51. Metabolism studies showed a higher and faster penetration of glufosinate in line T-549 than in line T-590. LC–TOF/MS analysis of glufosinate metabolism at 48h after herbicide treatment (300gaiha?1) revealed an 83.4% conversion of the herbicide (66.5% in N-acetyl-glufosinate metabolite), while in line T-549 conversion of the herbicide was about 40% (0% to N-acetyl-glufosinate). These results suggest that metabolism of glufosinate by the bar gene is a key mechanism of resistance in line T-590 that explains such high levels of herbicide tolerated by the plant, together with other mechanisms due to unmodified pathway, absorption and loss of glufosinate affinity for its target site.
The metabolism of glufosinate in the T-590 wheat cultivar is a key mechanism of resistance that explains such high levels of herbicide tolerated by the plant. A=Glufosinate; B=PPO; C=N-acetyl-glufosinate; D=MHB; E=MPB; F=MPP.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Brice M. Mba’ning , Bruno N. Lenta , Diderot T. Noungoué , Cyril Antheaume , Yanick F. Fongang , Silvère A. Ngouela , Fabrice F. Boyom , Philip J. Rosenthal , Etienne Tsamo , Norbert Sewald , Hartmut Laatsch Phytochemical investigation of the seeds of Salacia longipes var. camerunensis led to the isolation of four sesquiterpenoid derivatives, salaterpene A (1) (1?,2?,8?-triacetoxy-6?,9?-dibenzoyloxy-4?-hydroxy-dihydro-?-agarofuran), salaterpene B (2) (1?,2?,8?-triacetoxy-9?-benzoyloxy-6?-cinnamoyloxy-4?-hydroxy-dihydro-?-agarofuran), salaterpene C (3) (1?,2?-diacetoxy-6?,9?-dibenzoyloxy-4?-hydroxy-dihydro-?-agarofuran) and salaterpene D (4) (2?-acetoxy-1?,6?-dibenzoyloxy-4?-hydroxy-9?-nicotinoyloxy-dihydro-?-agarofuran) together with two known compounds (5 and 6). The structures of the compounds were established by means of NMR spectroscopy. Compounds 1–4 and 6 were tested in vitro for their antiplasmodial activity against Plasmodium falciparum chloroquine-resistant strain W2. All the tested compounds exhibited a moderate potency with IC50 below 2.7?M.
Four sesquiterpenoid derivatives, salaterpene A–E (1–4) together with two known compounds were isolated from the CH2Cl2–MeOH (1:1) extract of the seeds of Salacia longipes var. camerunensis. The isolates exhibited moderate potency in vitro against Plasmodium falciparum chloroquine- resistant strain W2 with IC50 below 2.7?M.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Lienhard Mack , Petra Gros , Jens Burkhardt , Karlheinz Seifert The feeding of Spodoptera littoralis and Autographa gamma caterpillars on tansy leaves led to a complete different release of volatile monoterpenes, sesquiterpenes, and hexenyl alkanoates. Volatiles were collected from S. littoralis and A. gamma larvae damaged, mechanically wounded, and excised tansy leaves by closed loop stripping analysis. The qualitative and quantitative determination of the volatiles were done by GC–MS- and GC-measurements. The oligosaccharides sucrose, raffinose, stachyose, and verbascose have been detected in oral secretion of the caterpillars of the cotton leafworm S. littoralis. When applied to damaged leaves of tansy plants, these oligosaccharides induce the tansy leaves to emit a similar volatile blend as the feeding of S. littoralis larvae.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Guo-Cai Wang , Guo-Qiang Li , Hua-Wei Geng , Tao Li , Jiao-Jiao Xu , Fang Ma , Xia Wu , Wen-Cai Ye , Yao-Lan Li Ten eudesmane-type sesquiterpene derivatives (1–10), including six cuauhtemone derivatives (1–6), one di-norsesquiterpene (3-oxo-di-nor-eudesma-4-en-11-oic acid, 7), and three eudesmane glycosides (alatoside F–H, 8–10) were isolated from the whole plants of Laggera alata together with 12 known compounds. Their structures were elucidated on the basis of extensive spectroscopic analysis, acid hydrolysis, and compounds 1 and 7 were studied by single-crystal X-ray diffraction analysis. The absolute configuration of 1 was determined by the application of the modified Mosher’s method. All of the isolated eudesmane-type sesquiterpenes were evaluated for their cytotoxic activities on six human cancer cell lines, but all of the compounds were inactive on the tested cell lines in the concentration of 100?g/mL.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Yukiko Matsuo , Nana Akagi , Chisato Hashimoto , Fumito Tachikawa , Yoshihiro Mimaki Examination of the bulbs of Bessera elegans (Liliaceae) led to isolation of nine new and five known steroidal glycosides. The structures of the nine compounds were determined based on the results of spectroscopic analysis, including two-dimensional NMR, and hydrolysis followed by chromatographic and spectroscopic analysis. The isolated compounds and derivatives were evaluated for cytotoxicity against HL-60 human promyelocytic leukemia cells, A549 human lung adenocarcinoma cells, and TIG-3 normal human diploid fibroblasts. One compound, the pseudo-furostanol glycoside, induced apoptosis in HL-60 and A549 cells in a time-dependent manner and cell-cycle arrest at the G0/G1 phase in A549 cells.
Nine steroidal glycosides were isolated from bulbs of Bessera elegans. The pseudo-furostanol glycoside shown here induced apoptosis in HL-60 and A549 cells in a time-dependent manner and cell-cycle arrest at the G0/G1 phase in A549 cells.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Ilaria Cesari , Emerson Ferreira Queiroz , Quentin Favre-Godal , Laurence Marcourt , Gabriele Caccialanza , Paul F. Moundipa , Gloria Brusotti , Jean-Luc Wolfender The water maceration and methanolic extract of the stem barks of Diospyros bipindensis, which is a medicinal plant used in Cameroon by Baka pygmies, revealed a complex high-performance liquid chromatography (HPLC) profile primarily composed of coumarin and naphthoquinone glycosides. The methanolic and apolar extracts also exhibited significant antifungal activity on a TLC bioautography assay against Candida albicans. HPLC-microfractionation in 96-well plates combined with bioautography enabled the rapid localization of the antifungal compound that was identified by HPLC-PDA and HPLC-MS analysis as plumbagin. These on-line structural information were also used to dereplicate four known compounds. The isolation of the polar constituents from the methanolic extract enabled the identification of eleven other compounds also present in the traditional preparation, nine of which are reported for the first time. The structures of those compounds were elucidated by UV, NMR and HR-MS analysis.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Guy P.P. Kamatou , Ilze Vermaak , Alvaro M. Viljoen , Brian M. Lawrence Menthol is a cyclic monoterpene alcohol which possesses well-known cooling characteristics and a residual minty smell of the oil remnants from which it was obtained. Because of these attributes it is one of the most important flavouring additives besides vanilla and citrus. Due to this reason it is used in a variety of consumer products ranging from confections such as chocolate and chewing gum to oral-care products such as toothpaste as well as in over-the-counter medicinal products for its cooling and biological effects. Its cooling effects are not exclusive to medicinal use. Approximately one quarter of the cigarettes on the market contain menthol and small amounts of menthol are even included in non-mentholated cigarettes. Natural menthol is isolated exclusively from Mentha canadensis, but can also be synthesised on industrial scale through various processes. Although menthol exists in eight stereoisomeric forms, (?)-menthol from the natural source and synthesised menthol with the same structure is the most preferred isomer. The demand for menthol is high and it was previously estimated that the worldwide use of menthol was 30–32,000 metric tonnes per annum. Menthol is not a predominant compound of the essential oils as it can only be found as a constituent of a limited number of aromatic plants. These plants are known to exhibit biological activity in vitro and in vivo such as antibacterial, antifungal, antipruritic, anticancer and analgesic effects, and are also an effective fumigant. In addition, menthol is one of the most effective terpenes used to enhance the dermal penetration of pharmaceuticals. This review summarises the chemical and biological properties of menthol and highlights its cooling effects and toxicity.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Sandra Kleine , Caroline Müller Intraspecific chemical diversity is a common phenomenon especially found in shoots of essential oil-accumulating plant species. Abiotic factors can influence the concentration of essential oils, but the effects are inconsistent and little is known in how far these may vary within an individual and within species between chemotypes. Tanacetum vulgare L. occurs in various chemotypes that differ in the composition of mono- and sesquiterpenoids in their shoot tissues. We investigated how far shoot chemotype grouping is mirrored in root terpenoid profiles. Furthermore, we studied whether different fertilisation amounts influence the plant growth and morphological traits as well as the constitutive terpenoid concentration of leaves and roots of three chemotypes, trans-carvyl acetate, ?-thujone, and camphor, to different degrees. Shoot terpenoids were dominated by monoterpenoids, while the roots contained mainly sesquiterpenoids. The clear grouping in three chemotypes based on leaf chemistry was weakly mirrored in the root terpenoid composition. Furthermore, the leaf C/N ratio and the stem height differed between chemotypes. All plants responded to increased nutrient availability with increased total biomass and specific leaf area but decreased C/N and root/shoot ratios. Leaf terpenoid concentrations decreased with increasing fertiliser supply, independent of chemotype. In contrast to the leaves, the terpenoid concentrations of the roots were unaffected by fertilisation. Our results demonstrate that aboveground and belowground organs within a species can be under different selection pressures.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Samir A.M. Abdelgaleil , Matsumi Doe , Munehiro Nakatani Three phragmalin-type limonoids, swietephragmin H (1), swietephragmin I (2) and 11-hydroxyswietephragmin B (3), and a mexicanolide-type limonoid 2-hydroxy-6-deacetoxyswietenine (4), together with known compounds, 6-O-acetyl-2-hydroxyswietenin (5), 2-hydroxyswietenine (6), swietemahonin G (7), methyl 6-hydroxyangolensate (8) and 7-deacetoxy-7-oxogedunin (9) were isolated from the leaves of Swietenia mahogani (Meliaceae). Their structures were established by extensive NMR experiments in conjunction with mass spectrometry. The antifeedant activity of the isolated compounds was evaluated.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Mariana Gil , Rubén Bottini , Federico Berli , Mariela Pontin , María Fernanda Silva , Patricia Piccoli Ultraviolet-B solar radiation (UV-B) is an environmental signal with biological effects in plant tissues. Recent investigations have assigned a protective role of volatile organic compounds (VOCs) in plant tissues submitted to biotic and abiotic stresses. This study investigated VOCs in berries at three developmental stages (veraison, pre-harvest and harvest) of Vitis vinifera L. cv. Malbec exposed (or not) to UV-B both, in in vitro and field experiments. By Head Space-Solid Phase Micro Extraction–Gas Chromatography–Electron Impact Mass Spectrometry (HS-SPME–GC–EIMS) analysis, 10 VOCs were identified at all developmental stages: four monoterpenes, three aldehydes, two alcohols and one ketone. Monoterpenes increased at pre-harvest and in response to UV-B in both, in vitro and field conditions. UV-B also augmented levels of some aldehydes, alcohols and ketones. These results along with others from the literature suggest that UV-B induce grape berries to produce VOCs (mainly monoterpenes) that protect the tissues from UV-B itself and other abiotic and biotic stresses, and could affect the wine flavor. Higher emission of monoterpenes was observed in the field experiments as compared in vitro, suggesting the UV-B/PAR ratio is not a signal in itself.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Rajender Oddepally , Gopi Sriram , Lalitha Guruprasad Kunitz trypsin inhibitor was purified from the seeds of Trigonella foenum-graecum (TfgKTI) belonging to fabaceae family by ammonium sulphate precipitation, cation exchange, gel filtration and hydrophobic chromatography. Purity of the protein was analyzed by RP-HPLC and native-PAGE. SDS–PAGE analysis under reducing and non-reducing conditions showed that protein consists of a single polypeptide chain with molecular mass of approximately 20kDa. Mass spectroscopy analysis revealed that the intact mass of purified inhibitor is 19,842.154Da. One dimensional SDS gel was tryptically digested, resulting peptides were subjected to MALDI-TOF-MS analysis, and peptide mass fingerprinting (PMF) analysis of TfgKTI shows sequence similarity with Kunitz trypsin inhibitor in database search. Two dimensional electrophoresis identified presence of four isoinhibitors (pI values of 5.1, 5.4, 5.7 and 6.1). Kinetic studies showed that the protein is a competitive inhibitor and has high binding affinity with trypsin (Ki 3.01×10?9M) and chymotrypsin (Ki 0.52×10?9M). The TfgKTI retained the inhibitory activity over a broad range of pH (pH 3–10), temperature (37–100°C) and salt concentration (up to 3.5%). Far-UV circular dichroism measurements revealed that TfgKTI is predominantly composed of ?-sheets (39%) and unordered structures (48%) with slight helical content (13%). TfgKTI retained over 90% trypsin inhibition upon storage at 4°C for over a period of six months.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Mohamed A. Farag , Maximilian Weigend , Federico Luebert , Grischa Brokamp , Ludger A. Wessjohann Several species of the genus Urtica (especially Urtica dioica, Urticaceae), are used medicinally to treat a variety of ailments. To better understand the chemical diversity of the genus and to compare different accessions and different taxa of Urtica, 63 leaf samples representing a broad geographical, taxonomical and morphological diversity were evaluated under controlled conditions. A molecular phylogeny for all taxa investigated was prepared to compare phytochemical similarity with phylogenetic relatedness. Metabolites were analyzed via UPLC–PDA–MS and multivariate data analyses. In total, 43 metabolites were identified, with phenolic compounds and hydroxy fatty acids as the dominant substance groups. Principal component analysis (PCA) and hierarchical clustering analysis (HCA) provides a first structured chemotaxonomy of the genus. The molecular data present a highly resolved phylogeny with well-supported clades and subclades. U. dioica is retrieved as both para- and polyphyletic. European members of the U. dioica group and the North American subspecies share a rather similar metabolite profile and were largely retrieved as one, nearly exclusive cluster by metabolite data. This latter cluster also includes – remotely related – Urtica urens, which is pharmaceutically used in the same way as U. dioica. However, most highly supported phylogenetic clades were not retrieved in the metabolite cluster analyses. Overall, metabolite profiles indicate considerable phytochemical diversity in the genus, which largely falls into a group characterized by high contents of hydroxy fatty acids (e.g., most Andean-American taxa) and another group characterized by high contents of phenolic acids (especially the U. dioica-clade). Anti-inflammatory in vitro COX1 enzyme inhibition assays suggest that bioactivity may be predicted by gross metabolic profiling in Urtica.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Yongji Lai , Yongbo Xue , Mengke Zhang , Jinwen Zhang , Wei Tang , Junjun Liu , Liang Lei , Juming Yan , Zengwei Luo , Jianping Zuo , Yan Li , Guangmin Yao , Yonghui Zhang Nine germacrane sesquiterpenoids with an unusual ?3-15,6-lactone moiety, scapiformolactones A–I (1–9), and one known seco-germacrane sesquiterpenoid, 3,7,11-trimethyldodeca-l,6,9-triene-3,11-diol (10), were isolated from whole plants of Salvia scapiformis Hance. Their structures were elucidated by spectroscopic methods including HR-ESIMS, IR, UV, NMR, and CD, as well as by quantum mechanical calculations and chemical transformations. Structures of compounds 1–3 were also confirmed by single-crystal X-ray diffraction analysis. Six germacrane 6,15-diol derivatives (11–16) were obtained by chemical transformation. Compounds 1–9 and 11–16 were evaluated for their in vitro immunomodulatory effects on T and B cells, as well as their in vitro cytotoxicity against five human cancer cell lines, HL-60, SMMC-7721, A-549, MCF-7, and SW480.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Jean-Luc Cacas , Corinne Buré , Fabienne Furt , Jean-Paul Maalouf , Alain Badoc , Stéphanie Cluzet , Jean-Marie Schmitter , Elvire Antajan , Sébastien Mongrand Although Glycosyl-Inositol-Phospho-Ceramides (GIPCs) are the main sphingolipids of plant tissues, they remain poorly characterized in term of structures. This lack of information, notably with regard to polar heads, currently hampers the understanding of GIPC functions in biological systems. This situation prompted us to undertake a large scale-analysis of plant GIPCs: 23 plant species chosen in various phylogenetic groups were surveyed for their total GIPC content. GIPCs were extracted and their polar heads were characterized by negative ion MALDI and ESI mass spectrometry. Our data shed light on an unexpected broad diversity of GIPC distributions within Plantae, and the occurrence of yet-unreported GIPC structures in green and red algae. In monocots, GIPCs with three saccharides were apparently found to be major, whereas a series with two saccharides was dominant in Eudicots within a few notable exceptions. In plant cell cultures, GIPC polar heads appeared to bear a higher number of glycan units than in the tissue from which they originate. Perspectives are discussed in term of GIPC metabolism diversity and function of these lipids.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Aparna Misra , Kasim Khan , Abhishek Niranjan , Pravendra Nath , Vidhu A. Sane The increasing consumption of fossil fuels and petroleum products is leading to their rapid depletion and is a matter of concern around the globe. Substitutes of fossil fuels are required to sustain the pace of economic development. In this context, oil from the non food crops (biofuel) has shown potential to substitute fossil fuels. Jatropha curcas is an excellent shrub spread and naturalized across the globe. Its oil contains a high percentage of unsaturated fatty acids (about 78–84% of total fatty acid content) making the oil suitable for biodiesel production. Despite its high oil content, it has been poorly studied in terms of important enzymes/genes responsible for oil biosynthesis. Here, we describe the isolation of the full length cDNA clone of JcDGAT1, a key enzyme involved in oil biosynthesis, from J. curcas seeds and manipulation of oil content and composition in transgenic Arabidopsis plants by its expression. Transcript analysis of JcDGAT1 reveals a gradual increase from early seed development to its maturation. Homozygous transgenic Arabidopsis lines expressing JcDGAT1 both under CaMV35S promoter and a seed specific promoter show an enhanced level of total oil content (up by 30–41%) in seeds but do not show any phenotypic differences. In addition, our studies also show alterations in the oil composition through JcDGAT1 expression. While the levels of saturated FAs such as palmitate and stearate in the oil do not change, there is significant reproducible decrease in the levels of oleic acid and a concomitant increase in levels of linolenic acid both under the CaMV35S promoter as well as the seed specific promoter. Our studies thus confirm that DGAT is involved in flux control in oil biosynthesis and show that JcDGAT1 could be used specifically to manipulate and improve oil content and composition in plants.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Alessio Cimmino , Anna Andolfi , Maria Chiara Zonno , Fabiana Avolio , Alexander Berestetskiy , Maurizio Vurro , Antonio Evidente Three tetrasubstituted furopyrans, named chenopodolans A–C, were isolated together with the well known fungal metabolite (?)-(R)-6-hydroxymellein from the liquid culture of Phoma chenopodiicola, a fungal pathogen proposed for the biological control of Chenopodium album, a common worldwide weed of arable crops. The structures of chenopodolans A–C were established by spectroscopic and chemical methods as 2-(3-methoxy-2,6-dimethyl-7aH-furo[2,3-b]pyran-4-yl)-butane-2,3-diol, 1-(3-methoxy-2,6-dimethyl-7aH-furo[2,3-b]pyran-4-yl)ethanol and 3-methoxy-2,6-dimethyl-4-(1-methylpropenyl)-7aH-furo[2,3-b]pyran, respectively. The absolute configuration R to the hydroxylated secondary carbon (C-11) of the side chain at C-4 of chenopodolan A was determined by applying an advanced Mosher’s method. Assayed by leaf puncture on host and non-host weeds chenopodolans A and B, and the 11-O-acetylchenopodolan A showed a strong phytotoxicity. These results showed that the nature of the side chain attached to C-4 is an important feature for the phytotoxicity. A weak zootoxic activity was only showed by chenopodolan B.
Publication date: Available online 3 December 2013 Source:Phytochemistry Author(s): Diana Molina , Luisa Patiño , Mónica Quintero , José Cortes , Sara Bastos The coffee berry borer Hypothenemus hampei is a pest that causes great economic damage to coffee grains worldwide. Because the proteins consumed are digested by aspartic proteases in the insect’s midgut, the inhibition of these proteases by transferring a gene encoding an aspartic protease inhibitor from Lupinus bogotensis Benth. to coffee plants could provide a promising strategy to control this pest. Five aspartic protease inhibitors from L. bogotensis (LbAPI) were accordingly purified and characterized. The gene encoding the L. bogotensis aspartic protease inhibitor (LbAPI), with the highest inhibitory activity against H. hampei, was expressed in Escherichia coli and the purified recombinant protein (rLbAPI), with a molecular mass of 15kDa, was subsequently assessed for its ability to inhibit the aspartic protease activity present in the H. hampei midgut in vitro, as well as its effects on the growth and development of H. hampei in vivo. The in vitro experiments showed that rLbAPI was highly effective against aspartic proteases from H. hampei guts, with a half maximal inhibitory concentration (IC50) of 2.9?g. The in vivo experiments showed that the concentration of rLbAPI (w/w) in the artificial diet necessary to cause 50% mortality (LD50) of the larvae was 0.91%. The amino acid sequence of LbAPI had high homology (52–80%) to the seed storage proteins, vicilin and ?-conglutin, suggesting that this protein was generated by evolutionary events from a ?-conglutin precursor. Based on these results, LbAPI may have a dual function as storage protein, and as defense protein against H. hampei. These results provide a promising alternative to obtain a coffee plant resistant to H. hampei.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Keisuke Nishikawa , Hiroshi Fukuda , Masato Abe , Kazunari Nakanishi , Yuta Tazawa , Chihiro Yamaguchi , Syuntaro Hiradate , Yoshiharu Fujii , Katsuhiro Okuda , Mitsuru Shindo 1-O-cis-Cinnamoyl-?-d-glucopyranose is known to be one of the most potent allelochemical candidates and was isolated from Spiraea thunbergii Sieb by Hiradate et al. (2004), who suggested that it derived its strong inhibitory activity from cis-cinnamic acid, which is crucial for phytotoxicity. In this study, key structural features and substituent effects of cis-cinnamic acid (cis-CA) on lettuce root growth inhibition was investigated. These structure–activity relationship studies indicated the importance of the spatial relationship of the aromatic ring and carboxylic acid moieties. In this context, conformationally constrained cis-CA analogues, in which the aromatic ring and cis-olefin were connected by a carbon bridge, were designed, synthesized, and evaluated as plant growth inhibitors. The results of the present study demonstrated that the inhibitory activities of the five-membered and six-membered bridged compounds were enhanced, up to 0.27?M, and were ten times higher than cis-CA, while the potency of the other compounds was reduced.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Chang-Qing Yang , Xiu-Ming Wu , Ju-Xin Ruan , Wen-Li Hu , Yin-Bo Mao , Xiao-Ya Chen , Ling-Jian Wang Cotton plants accumulate gossypol and related sesquiterpene aldehydes, which function as phytoalexins against pathogens and feeding deterrents to herbivorous insects. However, to date little is known about the biosynthesis of volatile terpenes in this crop. Herein is reported that 5 monoterpenes and 11 sesquiterpenes from extracts of a glanded cotton cultivar, Gossypium hirsutum cv. CCRI12, were detected by gas chromatography–mass spectrometry (GC–MS). By EST data mining combined with Rapid Amplification of cDNA Ends (RACE), full-length cDNAs of three terpene synthases (TPSs), GhTPS1, GhTPS2 and GhTPS3 were isolated. By in vitro assays of the recombinant proteins, it was found that GhTPS1 and GhTPS2 are sesquiterpene synthases: the former converted farnesyl pyrophosphate (FPP) into ?-caryophyllene and ?-humulene in a ratio of 2:1, whereas the latter produced several sesquiterpenes with guaia-1(10),11-diene as the major product. By contrast, GhTPS3 is a monoterpene synthase, which produced ?-pinene, ?-pinene, ?-phellandrene and trace amounts of other monoterpenes from geranyl pyrophosphate (GPP). The TPS activities were also supported by Virus Induced Gene Silencing (VIGS) in the cotton plant. GhTPS1 and GhTPS3 were highly expressed in the cotton plant overall, whereas GhTPS2 was expressed only in leaves. When stimulated by mechanical wounding, Verticillium dahliae (Vde) elicitor or methyl jasmonate (MeJA), production of terpenes and expression of the corresponding synthase genes were induced. These data demonstrate that the three genes account for the biosynthesis of volatile terpenes of cotton, at least of this Upland cotton.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Ilana Cruz-Silva , Christiane Neuhof , Andrezza Justino Gozzo , Viviane Abreu Nunes , Izaura Yoshico Hirata , Misako Uemura Sampaio , Rita de Cássia Figueiredo-Ribeiro , Heinz Neuhof , Mariana da Silva Araújo Acute lung injury (ALI) is characterized by neutrophil infiltration and the release of proteases, mainly elastase (NE), cathepsin G (Cat G) and proteinase 3 (PR3), which can be controlled by specific endogenous inhibitors. However, inhibitors of these proteases have been isolated from different sources, including plants. For this study, CeEI, or Caesalpinia echinata elastase inhibitor, was purified from C. echinata (Brazil-wood) seeds after acetone fractionation, followed by ion exchange and reversed phase chromatographic steps. Characterization with SDS–PAGE, stability assays, amino acid sequencing and alignment with other protein sequences confirmed that CeEI is a member of the soybean Kunitz trypsin inhibitor family. Like other members of this family, CeEI is a 20kDa monomeric protein; it is stable within a large pH and temperature range, with four cysteine residues forming two disulfide bridges, conserved amino acid residues and leucine-isoleucine residues in the reactive site. CeEI was able to inhibit NE and Cat G at a nanomolar range (with Kis of 1.9 and 3.6nM, respectively) and inhibited PR3 within a micromolar range (Ki 3.7?M), leading to hydrolysis of specific synthetic substrates. In a lung edema model, CeEI reduced the lung weight and pulmonary artery pressure until 180min after the injection of zymosan-activated polymorphonuclear neutrophils. In experiments performed in the presence of a Cat G and PR3, but not an NE inhibitor, lung edema was reduced only until 150min and pulmonary artery pressure was similar to that of the control. These results confirm that NE action is crucial to edema establishment and progression. Additionally, CeEI appears to be a useful tool for studying the physiology of pulmonary edema and provides a template for molecular engineering and drug design for ALI therapy.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Jie-Qing Liu , Yuan-Feng Yang , Xu-Yang Li , En-Qian Liu , Zhong-Rong Li , Lin Zhou , Yan Li , Ming-Hua Qiu Twelve rhamnofolane diterpenoids, including curcusecons A–E with unusual seco-rhamnofolane skeletons, curcusones F–J, 4-epi-curcusone E, and 3-dehydroxy-2-epi-caniojane, together with seven known analogues, curcusones A–E, jatrogrossidione, and 2-epi-jatrogrossidione, were isolated from the roots of Jatropha curcas. Their structures were determined by extensive spectroscopic methods, and the relative stereochemistry of curcusecon B was further confirmed by X-ray crystallographic data. Their cytotoxity against five human cancer cells was studied and the results indicated that the dienone system in ring B was essential for cytotoxicity of these compounds.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Emanuela Giacomelli , Samuel Bertrand , Andreas Nievergelt , Vincent Zwick , Claudia Simoes-Pires , Laurence Marcourt , Elisabeth Rivara-Minten , Muriel Cuendet , Angela Bisio , Jean-Luc Wolfender NMR and NP-HPLC-UV profiling of the exudate of Salvia corrugata revealed that its secondary metabolite composition was largely dominated by ?-hydroxy-?-isopropyl-benzoquinone diterpenoids. Among them, four diterpenes not described previously were isolated and identified as fruticulin C (3), 7?-methoxy-19-acetoxy-royleanone (4), 7?,19-diacetoxy-royleanone (5), and 7-dehydroxy-conacytone (7). In addition, the known diterpenes fruticulin A (1), demethyl-fruticulin A (2) and 7?-O-methyl-conacytone (6) were also obtained. The isolated compounds were evaluated for their cancer chemopreventive activity by measuring quinone reductase induction activity and histone deacetylase inhibition. Three compounds (1, 2 and 5) showed promising activity.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Hye Lin Park , Sang-Won Lee , Ki-Hong Jung , Tae-Ryong Hahn , Man-Ho Cho Rice produces diterpenoid and flavonoid phytoalexins for defense against pathogen attack. The production of phytoalexins in rice is also induced by UV-irradiation. To understand the metabolic networks involved in UV-induced phytoalexin biosynthesis and their regulation, phytochemical and transcriptomic analyses of UV-treated rice leaves were performed. In response to UV treatment, the accumulation of flavonoids was observed in rice leaves, which may serve as antioxidants against UV-induced oxidative stress. The phytochemical analysis confirmed sakuranetin accumulation and also demonstrated the induction of phenylamide synthesis in rice leaves by UV-irradiation. Transcriptomic analysis established that aromatic amino acid biosynthetic genes were immediately up-regulated after UV treatment. The genes involved in the phenylpropanoid pathway and flavonoid biosynthesis were also up-regulated. These findings suggest that the aromatic amino acid and flavonoid biosynthetic pathways are coordinately activated for the production of flavonoids and phenolic phytoalexins such as sakuranetin and phenylamides. An in silico analysis of UV-induced O-methyltransferase and acyltransferase genes suggested that these genes may be implicated in sakuranetin and phenylamide synthesis, respectively. The transcriptomic analysis also showed up-regulation of both methylerythritol phosphate pathway and the diterpenoid phytoalexin biosynthetic genes in response to UV treatment. A functional gene network analysis of phytoalexin biosynthetic and UV-induced genes for signaling components and transcription factors using RiceNet suggested that regulatory networks comprising signal perceiving receptor kinases, G-proteins, signal transducing mitogen-activated protein kinases and calcium signaling components, and transcription factors control flavonoid and phytoalexin biosynthesis in rice leaves under UV-C stress conditions.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Martha Leyte-Lugo , Mario Figueroa , María del Carmen González , Anthony E. Glenn , Martín González-Andrade , Rachel Mata An extract of the solid cultures of Sporormiella minimoides (Sporormiaceae) isolated as an endophytic fungus from Hintonia latiflora (Rubiaceae), yielded three polyketides, 3,6-dimethoxy-8-methyl-1H,6H-benzo[de]isochromene-1,9-dione, 3-hydroxy-1,6,10-trimethoxy-8-methyl-1H,3H-benzo[de]isochromen-9-one, and 5-hydroxy-2,7-dimethoxy-8-methylnaphthoquinone, along with three known compounds, corymbiferone, ziganein, and brocaenol B. Their structures were characterized by spectrometric and spectroscopic methods. So as to be consistent the literature reports, 3,6-dimethoxy-8-methyl-1H,6H-benzo[de]isochromene-1,9-dione and 3-hydroxy-1,6,10-trimethoxy-8-methyl-1H,3H-benzo[de]isochromen-9-one were given the trivial names of corymbiferone C and corymbiferan lactone E, respectively. All isolates were tested as potential human calmodulin (hCaM) inhibitors using the fluorescent biosensor hCaM V91C-mBBr, but only 5-hydroxy-2,7-dimethoxy-8-methylnaphthoquinone quenched significantly the extrinsic fluorescence of this biosensor, with a dissociation constant (Kd) value of 1.55?M. Refined docking analysis predicted that 5-hydroxy-2,7-dimethoxy-8-methylnaphthoquinone could also be bound to hCaM at site I displaying hydrophobic interactions with Phe19 and 68, Met51, 71, and 72, and Ile52 and 63 residues.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Tomohiro Minakawa , Kazufumi Toume , Midori A. Arai , Takashi Koyano , Thaworn Kowithayakorn , Masami Ishibashi In a screening program for bioactive natural products which can overcome Tumor necrosis factor (TNF)-related apoptosis-inducing ligand (TRAIL)-resistance, three prenylflavonoids, named pannokin A–C, were isolated from a MeOH extract of Artocarpus champeden (Moraceae) roots, together with three known prenylflavonoids. The structures of pannokin A–C were elucidated by spectroscopic analysis. These of the prenylflavonoids in combination with TRAIL, showed cytotoxic activity in sensitizing TRAIL-resistant human gastric adenocarcinoma (AGS) cells. Of these compounds, heterophyllin increased caspase 3/7 activity when combined with TRAIL in AGS cells, and enhanced the expression of DR4 and DR5 mRNA. Moreover, heterophyllin up-regulated mRNA expression of CCAAT/enhancer-binding protein-homologous protein (CHOP) which was reported to be an important regulator of DR5 expression. Thus, heterophyllin was presumed to cause a CHOP-dependent up-regulation of DR5 expression resulting in apoptosis in AGS cells.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Antonio Vassallo , Nunziatina De Tommasi , Irmgard Merfort , Rokia Sanogo , Lorella Severino , Marco Pelin , Roberto Della Loggia , Aurelia Tubaro , Silvio Sosa The leaves of Vernonia nigritiana Oliv. & Hiern. (Asteraceae) were investigated for their in vivo topical anti-inflammatory properties, following a bioassay-oriented fractionation approach. Petroleum ether, chloroform and chloroform–methanol extracts inhibited the Croton oil-induced ear dermatitis in mice. The chloroform extract was only about half as active as the non steroidal anti-inflammatory drug indomethacin (ID50=237 and 93?g/cm2, respectively). Phytochemical investigation of this extract led to the isolation of nine polyhydroxylated stigmasterol glycosides and six polyhydroxylated stigmasterols. Their structures were elucidated by NMR, MS and chemical methods. Each compound exerted a significant anti-oedema activity, the most active being 1 (3?-O-?-d-glucopyranosyloxy-5?-stigmasta-7,9(11),24(28)Z-triene-6?,16?,26,29-tetrol) and 3 (3?-O-?-d-glucopyranosyloxy-5?-stigmasta-7,9(11),24(28)Z-triene-6?,16?,29-triol), only two and five fold less potent than the steroidal drug hydrocortisone (ID50=0.10, 0.21 and 0.04?mol/cm2, respectively). Compound 1 (50?M) also completely inhibited the transcription factor NF-?B in vitro.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Liu Wenjian , Han Xiaoqiang , Xiao Yumei , Fan Jinlong , Zhang Yuanzhi , Lu Huizhe , Wang Mingan , Qin Zhaohai The plant hormone abscisic acid (ABA) plays a central role in the regulation of plant development and adaptation to environmental stress. The isomerization of ABA to the biologically inactive 2E-isomer by light considerably limits its applications in agricultural fields. To overcome this shortcoming, an ABA analogue, cis-2,3-cyclopropanated ABA, was synthesized, and its photostability and biological activities were investigated. This compound showed high photostability under UV light exposure, which was 4-fold higher than that of (±)-ABA. cis-2,3-cyclopropanated ABA exhibited high ABA-like activity, including the ability to effectively inhibit seed germination, seedling growth and stomatal movements of Arabidopsis. In some cases, its bioactivity approaches that of (±)-ABA. trans-2,3-cyclopropanated abscisic acid was also prepared, an isomer that was more photostable but which showed weak ABA-like activity.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Temine Sabudak , Ozlem Demirkiran , Mehmet Ozturk , Gulacti Topcu Two bischromones, 3,3?-dimethoxy-2?-oxychromone (1), 3,3?-dihydroxy-2,2?-oxychromone (2) and a biflavone, 5,7,4?,5?,3?,4??-hexahydroxy-3?-O-?-glucosyl-3?,7?-O-biflavone (3) have been isolated from whole plant of Trifolium echinatum Bieb. together with five known flavonoids. The structures of the compounds were elucidated by 1D and 2D NMR analysis as well as HRESIMS. The isolated compounds were investigated for their antioxidant activity and tyrosinase inhibitory activity. Highly potent inhibition was found for compounds 1 (IC50=0.41mM), 5 (IC50=0.47mM) and 8 (IC50=0.45mM) compared to those of standard tyrosinase inhibitors kojic acid (IC50=0.67mM) and l-mimosine (IC50=0.64mM). The antioxidative effect of the extracts was determined by using ?-carotene–linoleic acid, DPPH scavenging, ABTS+ scavenging, and CUPRAC assays. The experimental findings indicated that the compounds 2 and 8 were found to be active in radical scavenging and CUPRAC assays.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Yue Wang , Yan Sun , Chao Wang , Xiaokui Huo , Pinduan Liu , Changyuan Wang , Baojing Zhang , Libin Zhan , Houli Zhang , Sa Deng , Yanyan Zhao , Xiaochi Ma 11-Keto-?-boswellic acid (KBA), as one of the active constituents in the gum resin of Boswellia serrata, possesses significant biological activities including anti-inflammatory activity. However, its extensive metabolism and low polarity has limited the systemic availability of KBA. The present research was aimed to obtain and explore the various possible derivatives of KBA through biotransformation by Cunninghamella blakesleana AS 3.970. A total of ten transformed compounds were isolated and purified, and their chemical structures were characterized as 7?-hydroxy-11-keto-?-boswellic acid; 7?, 15?-dihydroxy-11-keto-?-boswellic acid ; 7?, 16?-dihydroxy-11-keto-?-boswellic acid; 7?, 16?-dihydroxy-11-keto-?-boswellic acid; 7?, 22?-dihydroxy-11-keto-?-boswellic acid; 7?, 21?-dihydroxy-11-keto-?-boswellic acid; 7?, 20?-dihydroxy-11-keto-?-boswellic acid; 7?, 30-dihydroxy-11-keto-?-boswellic acid; 3?, 7?-dihydroxy-11-oxours-12-ene-24, 30-dioic acid and 3?, 7?-dihydroxy-30-(2-hydroxypropanoyloxy)-11-oxours-12-en-24-oic acid by various spectroscopic methods. The biotransformation processes include hydroxylation, oxidation and esterification. Primary structure–activity relationships (SAR) of inhibitory effects on NO production in RAW 264.7 macrophage cells are discussed.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Anja Schramm , Samad Nejad Ebrahimi , Melanie Raith , Janine Zaugg , Diana C. Rueda , Steffen Hering , Matthias Hamburger An ethyl acetate extract of Curcuma kwangsiensis S.G. Lee & C.F. Liang (Zingiberaceae) rhizomes (100?g/ml) enhanced the GABA-induced chloride current (IGABA) through GABAA receptors of the ?1?2?2S subtype by 79.0±7.0%. Potentiation of IGABA was measured using the two-microelectrode voltage-clamp technique and Xenopus laevis oocytes. HPLC-based activity profiling of the crude extract led to the identification of 11 structurally related labdane diterpenoids, including four new compounds. Structure elucidation was achieved by comprehensive analysis of on-line (LC-PDA-ESI-TOF-MS) and off-line (microprobe 1D and 2D NMR) spectroscopic data. The absolute configuration of the compounds was established by comparison of experimental and calculated ECD spectra. Labdane diterpenes represent a new class of plant secondary metabolites eliciting positive GABAA receptor modulation. The highest efficiency was observed for zerumin A (maximum potentiation of IGABA by 309.4±35.6%, and EC50 of 24.9±8.8?M).
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Rama Narasimhan , Geliang Wang , Maoyin Li , Mary Roth , Ruth Welti , Xuemin Wang The availability of nitrogen (N) to plants has a profound impact on carbohydrate and protein metabolism, but little is known about its effect on membrane lipid species. This study examines the changes in galactolipid and phospholipid species in soybean as affected by the availability of N, either supplied to soil or obtained through Bradyrhizobium japonicum nodulation. When N was limited in soil, the content of galactolipids, monogalactosyldiacylglycerol (MGDG) and digalactosyldiacyglycerol (DGDG), decreased drastically in leaves, while a smaller decrease of DGDG was observed in roots. In both leaves and roots, the overall content of different phospholipid classes was largely unchanged by N limitation, although some individual phospholipid molecular species did display significant changes. Nodulation with Bradyrhizobium of soybean grown in N-deficient soil resulted in a large increase in levels of plastidic lipid classes, MGDG, DGDG, and phosphatidylglycerol, along with smaller increases in non-plastidic phospholipids in leaves. Nodulation also led to higher levels of phospholipids in roots without changes in root levels of MGDG and DGDG. Overall, N availability alters lipid content more in leaves than roots and more in galactolipids than phospholipids. Increased N availability leads to increased galactolipid accumulation in leaves, regardless of whether N is supplied from the soil or symbiotic fixation.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Hiroaki Kiyohara , Toshiake Matsuzaki , Haruki Yamada During screening for intestinal Peyer’s patch-immunomodulating polysaccharides from plant resources including medicinal herbs, a potent modulating activity was observed in a crude polysaccharide fraction (AS-1) from the rhizome of Anemarrhena asphodeloides Bunge. Oral administration of AS-1 (100mg/kg/day) to aged BALB/c mice enhanced productions of IL-10, IFN-? and IL-6 from Peyer’s patch immunocompetent cells, and its oral administration to ovalbumin (OVA)-fed B10.A mice led to significant suppression on induction of OVA-specific IgE in systemic immune system. Further fractionation of the polysaccharides in the crude polysaccharide fraction, AS-1, yielded 4 polysaccharide fractions that were potently active, and contained glucomannans. Treatment of these polysaccharide fractions with endo-?-d-(1?4)-mannanase significantly decreased their activities. Mannanase digestion of the active glucomannan gave both long and short hexosyl-oligosaccharides, whereas konjac glucomannan, which was inactive, released short oligosaccharides. Structural analysis indicates that the long oligosaccharides from the active glucomannan contain mannanase-resistant complex structure comprising ?-d-Man and ?-d-Glc.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Yuan-Yuan Cheng , Huan Chen , Hong-Ping He , Yu Zhang , Shi-Fei Li , Gui-Hua Tang , Ling-Li Guo , Wei Yang , Feng Zhu , Yong-Tang Zheng , Shun-Lin Li , Xiao-Jiang Hao Sixteen daphnane diterpenoids, trigothysoids A?P, along with 15 known ones, were isolated from the methanol extract of the twigs and leaves of Trigonostemon thyrsoideum. Their structures were established by extensive spectroscopic techniques, including 2D NMR spectroscopy and mass spectrometry. The anti-HIV-1 activity of the compounds was also evaluated in vitro, and five compounds demonstrated potent anti-HIV-1 activity, with EC50 values of 0.015–0.001nM and TI values of 1618–17,619.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Sanit Thongnest , Thitima Lhinhatrakool , Nuanchawee Wetprasit , Pakawadee Sutthivaiyakit , Somyote Sutthivaiyakit Six prenylated flavonoids, (2R,3S)-3,5,4?-trihydroxy-6?-6?dimethylpyrano(2?,3?:7,6)-8-(3??, 3??-dimethylallyl)flavanone, (2R,3S)-3,5,2?-trihydroxy-4?-methoxy-6?,6?-dimethylpyrano(2?,3?:7,6)-8-(3??,3??-dimethylallyl)flavanone, (2R,3R)-3,5,2?,4?-tetrahydroxy-6?,6?-dimethylpyrano(2?,3?:7,6)-8-(3??,3??-dimethylallyl)flavanone, 3,5,2?,4?-tetrahydroxy-6?,6?-dimethylpyrano(2?,3?:7,6)-8-(3??,3??-dimethylallyl)flavone, (2R,3R,2??R)-3,5,2??-trihydroxy-4?-methoxy-6?,6?-dimethylpyrano(2?,3?:7,6)-8-(3??-methylbut-3??-enyl)flavanone, (2R,3R)-3,5-dihydroxy-4?-methoxy-6?,6?-dimethylpyrano(2?,3?:7,6)-8-(2??,3??-epoxy-3??-methyl butyl)flavanone, an isoflavone, 6,7-dimethoxy-5,2?,4?-trihydroxyisoflavone, and octaeicosanyl-trans-p-coumarate together with 12 known compounds, were isolated from roots of Eriosema chinense. This structural elucidation was determined by spectroscopic methods. Several isolates and derivatives were evaluated for their antimicrobial and antioxidant activities. Results obtained provide additional evidence showing that the presence of both the free phenolic OH and the lipophilic prenyl groups are crucial for potent antimicrobial activity against yeast, gram positive and gram negative bacteria, whereas the presence of free phenolic OH group is required for strong radical scavenging property.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Nilton Syogo Arakawa , Leonardo Gobbo-Neto , Sérgio Ricardo Ambrosio , Gilmara Ausech Antonucci , Suely Vilela Sampaio , Mônica Tallarico Pupo , Suraia Said , Thomas J. Schmidt , Fernando Batista Da Costa Biotransformation of chemicals by microorganisms can be effective in increasing chemical diversity. Some fungi have been described to be useful for the biotransformation of sesquiterpene lactones. Nevertheless, in most cases, only minor or simple transformations of functional groups have been observed. Budlein A is a sesquiterpene lactone found in high amounts in American sunflower-like species of the genus Viguiera (Asteraceae). It shows important biological effects like in vitro and in vivo anti-inflammatory activity, as well as cytotoxicity against cancer cell lines. With the aim to obtain potentially bioactive derivatives of budlein A and taking into account that obtaining semi-synthetic analogues is a very complex task, the capability of soil fungi to promote biotransformation was investigated. In this work, the biotransformation of budlein A by the soil fungi Aspergillus terreus and A. niger affording three unusual sesquiterpenoid derivatives with carbon skeletons is reported. The chemical structures of the compounds were elucidated by 1D and 2D NMR spectrometry and HR-ESI-MS. The stereochemistry and molecular conformation of one derivative was assessed by molecular modeling techniques. The fungal metabolites displayed a reduced cytotoxicity against HL-60 cells when compared to the original natural product. The results show the versatility of microbial-catalyzed biotransformations leading to unusual derivatives.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Thiago M. Casella , Véronique Eparvier , Hugues Mandavid , Audrey Bendelac , Guillaume Odonne , Laura Dayan , Christophe Duplais , Laila S. Espindola , Didier Stien Because of the symbiotic nature of endophytes, this survey aims to investigate the probability of discovering antibacterial, antifungal and cytotoxic activities in leaf endophytic microbes. We isolated 138 cultivable microbes (121 fungi, 3 bacteria and 14 unidentified or unknown microbes) from 24 plant species, a significant relative proportion of which exhibited antifungal and cytotoxic potential against Candida albicans ATCC 10213 and the human cell lines KB (uterine cervical carcinoma), MDA-MB-435 (melanoma), and MRC5 (normal human lung fibroblasts). Three active fungal extracts were fractionated, resulting in the isolation of eight compounds. Seven had been described in the literature including the following: acremonisol A, semicochliodinol A, cochliodinol, griseofulvin, pyrenocin A, novae zelandin A and alterperylenol. A previously unreported compound named pyrrocidine C was isolated from Lewia infectoria SNB-GTC2402 and identified by spectroscopic analysis. As in pyrrocidines A and B, this compound is a cis-substituted decahydrofluorene with a quaternary carbon at C-5 and opposite stereochemistry at C-8 corresponding to C-6 of pyrrocidines A and B.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Mario A. Gómez-Hurtado , Fany E. Álvarez-Esquivel , Gabriela Rodríguez-García , Mauro M. Martínez-Pacheco , Rosa M. Espinoza-Madrigal , Teresa Pamatz-Bolaños , José L. Salvador-Hernández , Hugo A. García-Gutiérrez , Carlos M. Cerda-García-Rojas , Pedro Joseph-Nathan , Rosa E. del Río The dichloromethane extract from the leaves of Caesalpinia platyloba provided cassane diterpenes whose structures were determined as (?)-(5S,6R,8S,9S,10R,14R)-6-acetoxyvouacapane (1), (?)-(5S,6R,8S,9S,10R,12Z,14R)-6-acetoxycassa-12,15-diene (3), and (?)-(5S,6R,8S,9S,10R,13E)-6-acetoxycassa-13,15-diene (4). Compound 1 was chemically correlated with (?)-(5S,6R,8S,9S,10R,14R)-6-hydroxyvouacapane (2), (+)-(5S,8S,9S,10R,14R)-6-oxovouacapane (5), and (+)-(5S,6S,8S,9S,10R,14R)-6-acetoxyvouacapane (6), the last one previously isolated from Dipteryx lacunifera. The absolute configurations of all six diterpenes 1–6 were established by comparison of DFT calculated vibrational circular dicroism spectra of 1, 2 and 5 with those obtained experimentally. In addition, several reported chemical shifts for 2 and 5 were reassigned based on two-dimensional NMR measurements.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Xing-Fen Cao , Jun-Song Wang , Xiao-Bing Wang , Jun Luo , Hong-Ying Wang , Ling-Yi Kong Five monoterpene indole alkaloids, mitradiversifoline, with a unique rearranged skeleton, specionoxeine-N(4)-oxide, 7-hydroxyisopaynantheine, 3-dehydropaynantheine, and 3-isopaynantheine-N(4)-oxide, and 10 known ones, were isolated from Mitragyna diversifolia. All the isolates were evaluated for their inhibition of acetylcholinesterase activities, and four showed moderate activities, with IC50 values of 4.1, 5.2, 10.2, and 10.3?M, respectively.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Mohammed N.A. Khalil , Till Beuerle , Andreas Müller , Ludger Ernst , Vijaya B.R. Bhavanam , Benye Liu , Ludger Beerhues Aucuparin is the most widely distributed biphenyl phytoalexin in the rosaceous subtribe Pyrinae, which includes the economically important fruit trees apple and pear. The biphenyl scaffold is formed by biphenyl synthase, which catalyzes biosynthesis of 3,5-dihydroxybiphenyl. Conversion of this precursor to aucuparin (3,5-dimethoxy-4-hydroxybiphenyl) was studied in cell cultures of Sorbus aucuparia after treatment with an elicitor preparation from the scab-causing fungus Venturia inaequalis. The sequence of the biosynthetic steps detected was O-methylation – 4-hydroxylation – O-methylation. The two alkylation reactions were catalyzed by distinct methyltransferases, which differed in pH and temperature optima as well as stability. Biphenyl 4-hydroxylase was a microsomal cytochrome P450 monooxygenase, whose activity was appreciably decreased by the addition of established P450 inhibitors. When fed to V. inaequalis-treated S. aucuparia cell cultures, radioactively labeled 3,5-dihydroxybiphenyl was not only incorporated into aucuparin but also into the dibenzofuran eriobofuran, the accumulation of which paralleled that of aucuparin. However, biphenyl 2?-hydroxylase activity proposed to be involved in dibenzofuran formation was detected in neither microsomes nor cell-free extracts in the presence of NADPH and 2-oxoglutarate, respectively. Nevertheless, a basis for studying biphenyl biosynthesis at the gene level is provided.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Wirongrong Kaweetripob , Chulabhorn Mahidol , Hunsa Prawat , Somsak Ruchirawat Twenty-one triterpenes consisting of a lupane derivative, two friedelanes, an oleanane derivative, and 17 ursane-type triterpenoids, together with three known triterpenes, three sterols, a fatty acid, a sesquiterpene alkaloid, and a glycerol derivative, were isolated from the stem of Siphonodon celastrineus. Their structures were characterized by various spectroscopic techniques, as well as comparison with literature data. Twenty-seven metabolites of these were evaluated for cytotoxic activity against six human cancer cell lines. The biosynthetic formation of a 1,4-dioxane bridge is also discussed.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Sang Hee Park , Kwan Hee Park , Myeong Hwan Oh , Han Hyuk Kim , Kang In Choe , So Ra Kim , Kwang Jun Park , Min Won Lee Activity guided isolation of a Spiraea prunifolia extract yielded five caffeoyl hemiterpene glycosides: 4?-(6-O-caffeoyl-?-d-glucopyranosyl)-2?-methyl butyric acid, 1-O-caffeoyl-6-O-(4?-hydroxy-2?-methylene-butyroyl)-?-d-glucopyranoside, 1,2-O-dicaffeoyl-6-O-(4?-hydroxy-2?-methylene-butyroyl)-?-d-glucopyranoside, 1-O-caffeoyl-6-O-(4?-caffeoyl-2?-methylene-butyroyl)-?-d-glucopyranoside, and 1-O-caffeoyl-6-O-(4?-caffeoyl-3?-hydroxy-2?-methylene-butyroyl)-?-d-glucopyranoside, and nine known compounds. Structures were elucidated by analysis of 1D and 2D NMR spectra and FAB-MS. To evaluate the anti-oxidative and anti-inflammatory properties of all fourteen compounds, DPPH radical scavenging, NBT superoxide scavenging, and inhibition of nitric oxide production in LPS-stimulated RAW264.7 cells were examined. Three of the caffeoyl hemiterpene glycosides exhibited potent anti-oxidative and anti-inflammatory activities compared with Vitamin C and l-NMMA, which were used as positive controls.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Yoshiki Kashiwada , Yuka Omichi , Shin-ichiro Kurimoto , Hirofumi Shibata , Yoshiyuki Miyake , Tsukasa Kirimoto , Yoshihisa Takaishi Secoiridoid glucosides, including two conjugates with a phenolic and two conjugates with a nicotinic acid derivative (3 and 4), together with seven known secoiridoid derivatives, were isolated from flower buds of Lonicera japonica. The structures were elucidated by spectroscopic analyses. Anti-influenza activities of six isolated compounds were also evaluated by plaque assay and neuraminidase inhibitory assay.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Ivan R. Chechetkin , Alexander S. Blufard , Bulat I. Khairutdinov , Fakhima K. Mukhitova , Svetlana S. Gorina , Andrey Y. Yarin , Larisa L. Antsygina , Alexander N. Grechkin Two complex oxylipins (linolipins C and D) were isolated from the leaves of flax plants inoculated with phytopathogenic bacteria Pectobacterium atrosepticum. Their structures were elucidated based on UV, MS and NMR spectroscopic data. Both oxylipins were identified as digalactosyldiacylglycerol (DGDG) molecular species. Linolipin C contains one residue of divinyl ether (?5Z)-etherolenic acid and one ?-linolenate residue at sn-1 and sn-2 positions, respectively. Linolipin D possesses two (?5Z)-etherolenic acid residues at both sn-1 and sn-2 positions. The rapid formation (2–30min) of linolipins C and D alongside with linolipins A and B occurred in the flax leaves upon their damage by freezing–thawing.
Publication date: December 2013 Source:Phytochemistry, Volume 96 Author(s): Nicola Malafronte , Rokia Sanogo , Antonio Vassallo , Nunziatina De Tommasi , Giuseppe Bifulco , Fabrizio Dal Piaz Four pregnanes: 1-methoxy-pregnan-17(R)-1,4-dien-3,16-dione (1), 1-methoxy-pregnan-17(S)-1,4-dien-3,16-dione (2), 2,3-seco-pregnan-17(S)-2,3-dioic acid-16-oxo-dimethyl ester (4), 2?,3?,16?-trihydroxy-5?-pregnan-17(R)-20-yl acetate (7), three androstanes: 1-methoxy-androstan-1,4-dien-3,16-dione (3), 2,3-seco-androstan-2,3-dioic acid-16-oxo-dimethyl ester (5), 3-methoxycarbonyl-2,3-seco-androstan-3-oic acid-16-oxo-2,19-lactone (6), together with three known pregnane derivatives, were isolated from the roots of Trichilia emetica ssp. suberosa. Their structures were determined by means of 1D and 2D NMR spectroscopy, mass spectrometry analysis, as well as by quantum chemical calculations.
Posted on 5 December 2013 | 1:44 pm
Information about this site:
The author- or copyrights of
the listed Internet pages are held by
the respective authors or site
operators, who are also responsible for
the content of the presentations.
To see your page listed here: Send us an
eMail! Condition: Subject-related
content on chemistry, biochemistry and
comparable academic disciplines!