Phytochemistry

Current research reports and chronological list of recent articles.


Phytochemistry is the international scientific journal of pure and applied plant chemistry, plant biochemistry and molecular biology. It is also a is a primary source for papers dealing with plant secondary compounds, especially with regard to their biosynthesis and diverse properties.

The publisher is Elsevier. The copyright and publishing rights of specialized products listed below are in this publishing house. This is also responsible for the content shown.

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Additional research articles see Current Chemistry Research Articles. Magazines with similar content (phytochemistry):

 - Phytochemical Analysis.

 - Phytochemistry Letters.

 - Phytochemistry Reviews.



Phytochemistry - Abstracts



Diterpenes from Grangea maderaspatana

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Fang-Rong Chang, Shih-Ting Huang, Chih-Chuang Liaw, Ming-Hong Yen, Tsong-Long Hwang, Ching-Yeu Chen, Ming-Feng Hou, Shyng-Shiou Yuan, Yuan-Bin Cheng, Yang-Chang Wu

Phytochemical investigation of the ethanolic extract of Grangea maderaspatana led to isolation of gramaderins A–D, together with thirteen known compounds. All isolates were assayed for their anti-inflammatory activities. Consequently, 5,7-dihydroxy-3,6,3′,4′,5′-pentamethoxyflavone and 5,3′-dihydroxy-3,6,7,4′,5′-pentamethoxyflavone showed significant bioactivities by inhibiting superoxide anion generation. 8-Acetoxy-pentadeca-1,9Z,14-trien-4,6-diyne-3-ol also demonstrated potent inhibition on elastase release. The gramaderins A/C (β-alkyl linked γ-lactone) and gramaderins B/D (α-alkyl linked γ-lactone) co-exist in this plant material, of which the latter derivatives are few in nature. Gramaderins C/D possess a special linear dilactone diterpene skeleton, which never been reported.

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Datum: 30.09.2016


Current knowledge and future research perspectives on cassava (Manihot esculenta Crantz) chemical defenses: An agroecological view

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Delia M. Pinto-Zevallos, Martín Pareja, Bianca G. Ambrogi

Cassava (Manihot esculenta Crantz) is one of the most important staple crops worldwide. It constitutes the major source of carbohydrates for millions of low-income people living in rural areas, as well as a cash crop for smallholders in tropical and sub-tropical regions. The Food and Agriculture Organization of the United Nations predicts that cassava plantations will increase and production systems will intensify in the future, highlighting the need for developing strategies that improve the sustainability of production. Plant chemical defenses hold the potential for developing pest management strategies, as these plant traits can influence the behavior and performance of both pests and beneficial arthropods. Cassava plants are well-defended and produce a number of compounds involved in direct defense, such as cyanogenic glycosides, flavonoid glycosides, and hydroxycoumarins. In addition, volatile organic compounds induced upon herbivory and the secretion of extrafloral nectar act as indirect defense against herbivores by recruiting natural enemies. Here, cassava chemical defenses against pest arthropods are reviewed, with the aim of identifying gaps in our knowledge and areas of research that deserve further investigation for developing sound pest control strategies to improve sustainable production of this crop, and how these defenses can be used to benefit other crops. Cyanogenic content in cassava is also highly toxic to humans, and can cause irreversible health problems even at sub-lethal doses when consumed over prolonged periods. Therefore, the promotion of chemical defense in this crop should not aggravate these problems, and must be accompanied with the education on processing methods that reduce human exposure to cyanide.

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Datum: 30.09.2016


Bioactive ent-kaurane diterpenoids from Isodon serra

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Jun Wan, Miao Liu, Hua-Yi Jiang, Jin Yang, Xue Du, Xiao-Nian Li, Wei-Guang Wang, Yan Li, Jian-Xin Pu, Han-Dong Sun

Nine 7,20-epoxy-ent-kaurane diterpenoids (15-acetylmegathyrin B, serrin E, 14β-hydroxyrabdocoestin A, serrin F, serrin G, 11-epi-rabdocoestin A, serrin H, serrin I, and 15-acetylenanderianin N), along with seven known ones, were isolated from the aerial parts of Isodon serra. Their structures were elucidated by extensive spectroscopic analysis, and the absolute configuration of 15-acetylmegathyrin B was determined by signal-crystal X-ray diffraction. All of these compounds were evaluated for their cytotoxic activities against five human tumor cell lines (HL-60, SMMC-7721, A-549, MCF-7, SW480). Serrin F, rabdocoestin B and 1α,11β-dihydroxy-1α,11β-acetonide-7α,20-epoxy-ent-kaur-16-en-15-one showed cytotoxic activities against all cell lines, with IC50 values ranging from 0.7 to 4.6 μM; serrin F also strongly inhibited NO production in LPS-stimulated RAW264.7 cells. Otherwise, 14β-hydroxyrabdocoestin A, serrins H and I, as well as enanderianin N and megathyrin B, also exhibited inhibitory effects towards NO production, while no cytotoxicity against five cell lines was detected.

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Datum: 30.09.2016


Structure, anti-Phytophthora and anti-tumor activities of a nortriterpenoid from the rhizome of Phlomis purpurea (Lamiaceae)

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Maria C. Mateus, Dina Neves, Bruno Dacunha, Endre Laczko, Cristiana Maia, Rúben Teixeira, Alfredo Cravador

To investigate bioactive compounds potentially involved in the biotic interactions exhibited by Phlomis purpurea (Lamiaceae) in rhizospheres infested with Phytophthora cinnamomi, the plant rhizome was chemically analysed. The nortriterpenoid (17S)-2α,3α,11α,23,24-pentahydroxy-19(18 → 17)-abeo-28-norolean-12-en-18-one, was isolated and its structure was elucidated by comprehensive spectroscopic analysis, chiefly using 2D NMR experiments, and X-ray analysis. It was shown to be exuded by roots and to exhibit anti-Phytophthora and antitumor activities.

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Datum: 30.09.2016


Graphical Contents List

Publication date: November 2016
Source:Phytochemistry, Volume 131










Datum: 30.09.2016


Bioactive benzofuran-chalcanes as potential NQO1 inducers from Millettia pulchra (Benth) kurzvar-laxior (Dunn) Z.Wei

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Wenli Wang, Ning Li, Jian Wang, Gang Chen, Renbin Huang, Weihong Zhao, Jiayuan Li, Yingying Si

Five chalcanes ((αR)-2, α′-dimethoxy-furano-[4″, 5′′: 3′, 4′] chalcane, (αR, βR)-2′, α′, β-trimethoxy-furano-[4″, 5′′: 3′, 4′] chalcane, (αS, βR)-2′, α′, β-trimethoxy-furano-[4″, 5′′: 3′, 4′] chalcane, (αR, βR)-2′, β-dimethoxy-α′-hydroxyethoxy-furano-[4″, 5′′: 3′, 4′] chalcane, (αS, βR)-2′, β-dimethoxy-α′-hydroxyethoxy-furano-[4″, 5′′: 3′, 4′] chalcane) and a flavonoid glycoside (3′, 7-dihydroxy-6-methoxy-4′, 5′-methylenedioxyisoflavone 6-O-β-D- glucopyranoside), together with 15 known components, were isolated from the leaves of Millettia pulchra (Benth) Kurzvar-laxior (Dunn) Z. Wei, a traditional Zhuang medicine. Their chemical structures were established by extensive analysis of NMR, mass spectrometry and ECD spectra. Furthermore compounds (αR, βR)-2′, β-dimethoxy-α′-hydroxyethoxy-furano-[4″, 5′′: 3′, 4′] chalcane, (αS, βR)-2′, β-dimethoxy-α′-hydroxyethoxy-furano-[4″, 5′′: 3′, 4′] chalcane, quercetin, methyl 2-O-β-D-glucopyranosylbenzoate, 6,7-dimethoxy-3′,4′-methylenedioxyisoflavone and lyoniresinol were suggested to be potential chemopreventive agents because of their significant activity in inducing NQO1 ([NAD(P)H quinine oxidoreductase 1], a phase II metabolism enzyme).

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Datum: 30.09.2016


Phytochemical study and biological evaluation of chemical constituents of Platanus orientalis and Platanus × acerifolia buds

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Quoc Dang Thai, Job Tchoumtchoua, Maria Makropoulou, Athina Boulaka, Aggeliki K. Meligova, Dimitra J. Mitsiou, Sophia Mitakou, Sylvie Michel, Maria Halabalaki, Michael N. Alexis, Leandros A. Skaltsounis

One flavonol glycoside, two O-isoprenylated flavonols, one α,α-dimethylallyl flavonol, one dihydrochalcone, two furanocoumarins and one terpenoid previously undescribed, along with 42 known compounds were isolated from the buds of two European Platanaceae, Platanus orientalis and Platanus × acerifolia. Their chemical structures were elucidated on the basis of spectroscopic analysis, including homonuclear and heteronuclear correlation NMR (COSY, NOESY, HSQC, and HMBC) experiments, as well as HRMS data. The estrogen-like and antiestrogen-like activity of dichloromethane and methanol extracts of P. orientalis and P. × acerifolia buds and isolated compounds was evaluated using estrogen-responsive cell lines. The potency of selected estrogen agonists to regulate gene expression through ERα and/or ERβ was compared with their in vitro osteoblastogenic activity. Kaempferol and 8-C-(1,1-dimethyl-2-propen-1-yl)-5,7-dihydroxyflavonol displayed osteoblastogenic as well as ERα-mediated estrogenic activity similar to estradiol.

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Datum: 30.09.2016


Callistiviminenes A-O: Diverse adducts of β-triketone and sesqui- or monoterpene from the fruits of Callistemon viminalis

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Lin Wu, Xiao-bing Wang, Rui-jun Li, Ya-long Zhang, Ming-hua Yang, Jun Luo, Ling-Yi Kong

Callistiviminenes A-O, fifteen adducts of β-triketone with sesqui- or monoterpene, along with a known compound, were isolated from the fruits of Callistemon viminalis. Callistiviminenes A and B are β-triketone-coupled (−)-bicyclosequiphellandrene contained an oxaspiro[5.5]undecene unit, and callistiviminenes C-E are rare adducts of β-triketone and bicyclogermacrene. Their structures and absolute configurations were elucidated by spectroscopic and computational methods, as well as by single-crystal X-ray diffraction experiment. A plausible biosynthetic pathway to these compounds involves a hetero-Diels–Alder reaction. Callistiviminenes C and D exhibited inhibition against lipopolysaccharide-induced nitric oxide production in RAW 264.7 macrophages with IC50 value of 20.3 μM and 32.5 μM, respectively.

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Datum: 30.09.2016


Naming natural products: Uses, abuses and a proposal for discussion

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Catherine Lavaud, Georges Massiot








Datum: 30.09.2016


Editorial Board/Publication Information

Publication date: October 2016
Source:Phytochemistry, Volume 130










Datum: 30.09.2016


Botanical and biological pesticides elicit a similar Induced Systemic Response in tomato (Solanum lycopersicum) secondary metabolism

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Luca Pretali, Letizia Bernardo, Timothy S. Butterfield, Marco Trevisan, Luigi Lucini

Natural pesticides have attracted substantial interest due to the increase in organic agriculture and enhanced attention to environmental pollution. Plant Growth Promoting Bacteria (PGPB) are applied for both disease control and growth enhancement; PGPBs are known to elicit Induced Systemic Response (ISR) in plants. However, less is known about the effect of botanical pesticides, such as the azadirachtin-containing neem extracts, on plant metabolism. This study aimed to investigate the effects of foliar application of the above-mentioned natural pesticides on the metabolic profiling of tomato. Leaf application of Bacillus subtilis fostered Induced Systemic Resistance (ISR) in treated plants via the Jasmonic acid pathway, and enhanced production of secondary metabolites such as flavonoids, phytoalexins and auxins. Changes in sterols and terpenes, as well as an increase in glucosinolates were also observed. Interestingly, azadirachtin-treated tomatoes also showed an increase in ISR and our results revealed that most of the enriched metabolites are shared with a B. subtilis treatment, suggesting conserved biochemical responses. These (un)expected findings indicate that plants are not insensitive to application of natural pesticide and while Azadirachtin is applied as a direct pesticide, it also stimulates a defense response in tomatoes very similar to B. subtilis induced ISR.

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Datum: 30.09.2016


Carlactone-type strigolactones and their synthetic analogues as inducers of hyphal branching in arbuscular mycorrhizal fungi

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Narumi Mori, Kenta Nishiuma, Takuya Sugiyama, Hideo Hayashi, Kohki Akiyama

Hyphal branching in the vicinity of host roots is a host recognition response of arbuscular mycorrhizal fungi. This morphological event is elicited by strigolactones. Strigolactones are carotenoid-derived terpenoids that are synthesized from carlactone and its oxidized derivatives. To test the possibility that carlactone and its oxidized derivatives might act as host-derived precolonization signals in arbuscular mycorrhizal symbiosis, carlactone, carlactonoic acid, and methyl carlactonoate as well as monohydroxycarlactones, 4-, 18-, and 19-hydroxycarlactones, were synthesized chemically and evaluated for hyphal branching-inducing activity in germinating spores of the arbuscular mycorrhizal fungus Gigaspora margarita. Hyphal branching activity was found to correlate with the degree of oxidation at C-19 methyl. Carlactone was only weakly active (100 ng/disc), whereas carlactonoic acid showed comparable activity to the natural canonical strigolactones such as strigol and sorgomol (100 pg/disc). Hydroxylation at either C-4 or C-18 did not significantly affect the activity. A series of carlactone analogues, named AD ester and AA’D diester, was synthesized by reacting formyl Meldrum’s acid with benzyl, cyclohexylmethyl, and cyclogeranyl alcohols (the A-ring part), followed by coupling of the potassium enolates of the resulting formylacetic esters with the D-ring butenolide. AD ester analogues exhibited moderate activity (1 ng–100 pg/disc), while AA’D diester analogues having cyclohexylmethyl and cyclogeranyl groups were highly active on the AM fungus (10 pg/disc). These results indicate that the oxidation of methyl to carboxyl at C-19 in carlactone is a prerequisite but BC-ring formation is not essential to show hyphal branching activity comparable to that of canonical strigolactones.

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Datum: 30.09.2016


Identification of CYP82E21 as a functional nicotine N-demethylase in tobacco flowers

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Verena Liedschulte, Joanne Deborah Schwaar, Hélène Laparra, Aline Vuarnoz, Bérangère Philippon, Nicolas Bakaher, Nicolas Sierro, Lucien Bovet, Gerhard Lang, Simon Goepfert

In the tobacco plant, nicotine N-demethylase enzymes (NND) belonging to the cytochrome P450 family catalyse the conversion of nicotine to nornicotine, the precursor of the carcinogenic tobacco-specific N-nitrosamine, N-nitrosonornicotine. To date three demethylase genes, namely CYP82E4, CYP82E5 and CYP82E10, have been shown to be involved in this process, while the related CYP82E2 and CYP82E3 genes are not functional. We have identified a further gene named CYP82E21 encoding a putative nicotine N-demethylase closely related to the CYP82E genes. The CYP82E21 gene was found in all Nicotiana tabacum cultivars analysed and originates from the tobacco ancestor Nicotiana tomentosiformis. We show that, in contrast to all other previously characterized NND genes, CYP82E21 is not expressed in green or senescent leaves, but in flowers, more specifically in ovaries. The nicotine N-demethylase activity of CYP82E21 was confirmed by ectopic expression of the coding sequence in a tobacco line lacking functional CYP82E4, CYP82E5 and CYP82E10 genes, resulting in an eightfold increase of nicotine demethylation compared to the control plants. Furthermore, nornicotine formation can be reduced in ovaries by introducing a CYP82E21-specific RNAi construct. Together, our results demonstrate that the CYP82E21 gene encodes a functional ovary-specific nicotine N-demethylase.

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Datum: 30.09.2016


Nitric oxide inhibitory xanthones from the pericarps of Garcinia mangostana

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Qianyu Liu, Dan Li, Anqi Wang, Zhen Dong, Sheng Yin, Qingwen Zhang, Yang Ye, Liangchun Li, Ligen Lin

Mangosteen (Garcinia mangostana, Clusiaceae) is called “queen of fruit” in Southeast Asia. In the current study, three dimeric xanthones, garcinoxanthones A–C, and four monomeric xanthones, garcinoxanthones D–G, together with 18 known xanthones, were isolated from the pericarps of G. mangostana, collected in Thailand. The structures of garcinoxanthones A–G were elucidated by analysis of their 1D and 2D NMR and other spectroscopic data, and their absolute configurations were determined by the CD spectra. All seven compounds were tested for nitric oxide (NO) inhibitory activity on lipopolysaccharide (LPS)-stimulated RAW264.7 cells. Garcinoxanthones B and C significantly inhibited NO production with IC50 values of 11.3 ± 1.7 and 18.0 ± 1.8 μM, respectively, which were comparable with the positive control indomethacin (IC50 3.9 ± 0.3 μM). Moreover, garcinoxanthone B suppressed inducible NO synthase expression in a dose-dependent manner. These results reveal the presence of rare dimeric xanthones in G. mangostana and their NO inhibitory effect on LPS-stimulated murine macrophage cells.

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Datum: 30.09.2016


A volatolomic approach for studying plant variability: the case of selected Helichrysum species (Asteraceae)

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Claudia Giuliani, Lorenzo Lazzaro, Roberto Calamassi, Luca Calamai, Riccardo Romoli, Gelsomina Fico, Bruno Foggi, Marta Mariotti Lippi

The species of Helichrysum sect. Stoechadina (Asteraceae) are well-known for their secondary metabolite content and the characteristic aromatic bouquets. In the wild, populations exhibit a wide phenotypic plasticity which makes critical the circumscription of species and infraspecific ranks. Previous investigations on Helichrysum italicum complex focused on a possible phytochemical typification based on hydrodistilled essential oils. Aims of this paper are three-fold: (i) characterizing the volatile profiles of different populations, testing (ii) how these profiles vary across populations and (iii) how the phytochemical diversity may contribute in solving taxonomic problems. Nine selected Helichrysum populations, included within the H. italicum complex, Helichrysum litoreum and Helichrysum stoechas, were investigated. H. stoechas was chosen as outgroup for validating the method. After collection in the wild, plants were cultivated in standard growing conditions for over one year. Annual leafy shoots were screened in the post-blooming period for the emissions of volatile organic compounds (VOCs) by means of headspace solid phase microextraction coupled with gas-chromatography and mass spectrometry (HS-SPME-GC/MS). The VOC composition analysis revealed the production of overall 386 different compounds, with terpenes being the most represented compound class. Statistical data processing allowed the identification of the indicator compounds that differentiate the single populations, revealing the influence of the geographical provenance area in determining the volatile profiles. These results suggested the potential use of VOCs as valuable diacritical characters in discriminating the Helichrysum populations. In addition, the cross-validation analysis hinted the potentiality of this volatolomic study in the discrimination of the Helichrysum species and subspecies, highlighting a general congruence with the current taxonomic treatment of the genus. The consistency between this phytochemical approach and the traditional morphometrical analysis in studying the Helichrysum populations supports the validity of the VOC profile in solving taxonomic problems.

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Datum: 30.09.2016


Palhicerines A–F, Lycopodium alkaloids from the club moss Palhinhaea cernua

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Yu Tang, Juan Xiong, Yike Zou, Hai-Yan Zhang, Jin-Feng Hu

Four fawcettimine-type (palhicerines A–D, resp.) and two lycopodine-type (palhicerines E and F) Lycopodium alkaloids together with twenty known ones were isolated from the whole plant of Palhinhaea cernua. The structures and absolute configurations of the palhicerines A–F were determined by extensive spectroscopic methods, single-crystal X-ray diffraction analyses, chemical transformation, and electronic circular dichroism (ECD) calculations or induced electronic circular dichroism (IECD) spectra. Among the isolates, the new C/D-ring of the palhicerines A–C (trans-fused fawcettimine-type alkaloids) are rare, and each possesses a β-oriented C-16 methyl group and a distinctive tertiary methoxy group at C-13. Chemotaxonomy for differentiating species in the genus Palhinhaea is briefly discussed.

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Datum: 30.09.2016


Metabolic changes in Euphorbia palusrtis latex after fungal infection

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Gordana Krstić, Boban Anđelković, Young Hae Choi, Vlatka Vajs, Tatjana Stević, Vele Tešević, Dejan Gođevac

The variations of metabolic profile of the latex of wild-growing Euphorbia palustris was carried out using multivariate analysis of 1H NMR spectral data. One population was infected with fungi Fusarium sporotrichioides, Fusarium proliferatum and Alternaria alternata, while the other consisted of healthy plant species. The non-polar metabolites of latex extracts such as benzoyl ingenol-laurate, amyrin decadienoate esters, cis-1,4-polyisoprene, and 24-methylenecycloartanol were identified using 1H and 2D NMR spectra. Principal component analysis of 1H NMR data provided a clear discrimination between the latex of infected and healthy plants. Minimum inhibitory concentration and minimum fungicidal concentration values of the latex extracts of healthy and infected plants were determined. The latex of infected plants was found to contain higher levels of benzoyl ingenol-laurate and 24-methylenecycloartanol, of which concentrations were strongly correlated with the antifungal activities of the latex.

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Datum: 30.09.2016


Structures and biological activities of the triterpenoids and sesquiterpenoids from Alisma orientale

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Qingjuan Ma, Li Han, Xiaoxu Bi, Xingbo Wang, Yu Mu, Peipei Guan, Liya Li, Xueshi Huang

Sixteen triterpenoids and nine sesquiterpenoids were isolated from the rhizome of Alisma orientale. Structures of 16-oxo-11-anhydroalisol A 24-acetate, 13β,17β-epoxy-24,25,26,27-tetranor-alisol A 23-oic acid, 1αH,5αH-guaia-6-ene-4β,10β-diol, and alisguaiaone were elucidated by comprehensive spectroscopic data analysis. The cytotoxic, antibacterial, antifungal, anti-inflammatory, and α-glucosidase inhibitory activities of isolated terpenoids were evaluated. Triterpenoids alisol A, alisol A 24-acetate, 25-O-ethylalisol A, 11-deoxyalisol A, alisol E 24-acetate, alisol G, alisol B 23-acetate and sesquiterpenoids 1αH,5αH-guaia-6-ene-4β,10β-diol, 10-hydroxy-7,10-epoxysalvialane exhibited cytotoxicities against the three tested human cancer cell lines with IC50 values ranging from 11.5 ± 1.7 μM to 76.7 ± 1.4 μM. Triterpenoids alisol A, 25-O-ethylalisol A, 11-deoxyalisol A, alisol E 24-acetate, alisol G, and 25-anhydroalisol F showed antibacterial activities against the Gram-positive strains Bacillus subtilis and Staphylococcus aureus with MIC values of 12.5–100 μg/mL. Sesquiterpenoid 4β,10β-dihydroxy-1αH,5βH-guaia-6-ene exhibited antibacterial activity against B. subtilis with an MIC value of 50 μg/mL, and 10-hydroxy-7,10-epoxysalvialane exhibited activity against S. aureus with an MIC value of 100 μg/mL. Compounds 16-oxo-11-anhydroalisol A 24-acetate, alisol F, 25-anhydroalisol F, and alisguaiaone exhibited inhibitory effects on lipopolysaccharide-induced NO production in RAW 264.7 macrophage cells. None of the compounds showed obvious inhibitory activity against α-glucosidase.






Datum: 30.09.2016


Chemical characterization of high-molar-mass fractions in a Norway spruce knotwood ethanol extract

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Annika I. Smeds, Patrik C. Eklund, Stefan M. Willför

The low-molar-mass (LMM) fraction, only, i.e., the GC-eluting compounds, which are mainly lignans, has been characterized in Norway spruce knotwood hydrophilic extracts previously. Of this fraction, many lignans and sesquilignans and all GC peaks supposedly representing dilignans remain unidentified. In this work, dilignans and the GC non-eluting compounds (the high-molar mass fractions, HMM) were characterized in a 7-hydroxymatairesinol-reduced knotwood ethanol extract of Norway spruce by using several fractionation and analytical techniques. A methyl tert-butyl ether (MTBE) insoluble fraction of the extract contained mainly HMM material, of which the main part was shown to consist of lignan oligomers. The oligolignans (with a molar mass up to approximately 3700 Da) seemed to be linked by 55′ bonds, some of them containing one or two guaiacylglycerol ether units linked to the lignan by βO4 or β5 bonds. Several oligolignans were identified or tentatively identified. The MTBE soluble fraction, which accounted for the major part (81%) of the extract, contained mainly LMM material (lignans, sesqui- and dilignans). The part of the HMM material in the MTBE soluble fraction that was easily isolable (2%) seemed to contain polymers of fatty acids and alcohols, resin acids, and sterols.

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Datum: 30.09.2016


Spirostanol glycosides with hemostatic and antimicrobial activities from Trillium kamtschaticum

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Yu Chen, Wei Ni, Huan Yan, Xu-Jie Qin, Afsar Khan, Hui Liu, Tong Shu, Ling-Yu Jin, Hai-Yang Liu

Ten spirostanol glycosides, trillikamtosides A–J, together with eleven known analogues, were isolated from the hemostatic fraction of the 75% aqueous EtOH extract of the whole herbs of Trillium kamtschaticum. Their structures were established by extensive spectroscopic data analysis and chemical methods. The aglycones of three of these compounds had unique 3β,17α-dihydroxy-spirostanes featuring a double bond between C-4 and C-5, while two others represent a rare class of spirostanol glycosides which possess a 5(6 → 7) abeo-steroidal aglycone. All the compounds were evaluated for their hemostatic and antimicrobial activities. Three of the spirostanol glycosides exhibited induced-platelet aggregation at a concentration of 300 μg/mL with maximal induced-platelet aggregation rates of 72%, 71%, and 62% in rabbits, respectively, and their EC50 values were 492.7, 203.3, and 109.8 μM. Five of the spirostanol glycosides showed an anti-Candida albicans effect with MIC values of 21.1, 10.6, 8.8, 21.6, and 11.0 μM, respectively.

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Datum: 30.09.2016


Regulation of plant secondary metabolism and associated specialized cell development by MYBs and bHLHs

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): William R. Chezem, Nicole K. Clay

Plants are unrivaled in the natural world in both the number and complexity of secondary metabolites they produce, and the ubiquitous phenylpropanoids and the lineage-specific glucosinolates represent two such large and chemically diverse groups. Advances in genome-enabled biochemistry and metabolomic technologies have greatly increased the understanding of their metabolic networks in diverse plant species. There also has been some progress in elucidating the gene regulatory networks that are key to their synthesis, accumulation and function. This review highlights what is currently known about the gene regulatory networks and the stable sub-networks of transcription factors at their cores that regulate the production of these plant secondary metabolites and the differentiation of specialized cell types that are equally important to their defensive function. Remarkably, some of these core components are evolutionarily conserved between secondary metabolism and specialized cell development and across distantly related plant species. These findings suggest that the more ancient gene regulatory networks for the differentiation of fundamental cell types may have been recruited and remodeled for the generation of the vast majority of plant secondary metabolites and their specialized tissues.

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Datum: 30.09.2016


Graphical Contents List

Publication date: October 2016
Source:Phytochemistry, Volume 130










Datum: 30.09.2016


Editorial Board/Publication Information

Publication date: November 2016
Source:Phytochemistry, Volume 131










Datum: 30.09.2016


Saponins of Agave: Chemistry and bioactivity

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Jasmeen Sidana, Bikram Singh, Om P. Sharma

The genus Agave comprises more than 400 species with geographical presence in the tropical and sub-tropical regions of the world. These plants have a rich history of folkloric use and are known for a wide spectrum of applications. Secondary metabolites of diverse chemical classes have been reported from Agave species. Owing to their pharmacological significance, the steroidal saponins of Agave have caught the attention of phytochemists, biologists and drug discovery scientists. The present review describes 141 steroidal saponins and sapogenins and covers the literature published from 1970 to 2015. It is a comprehensive and coherent presentation of the structures, methods of chemical profiling, structure elucidation and biological activities of the saponins and sapogenins reported from Agave. The article provides a perspective of the research on steroidal compounds of Agave.

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Datum: 30.09.2016


Discrimination of wild types and hybrids of Duboisia myoporoides and Duboisia leichhardtii at different growth stages using 1H NMR-based metabolite profiling and tropane alkaloids-targeted HPLC-MS analysis

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Sophie Friederike Ullrich, Nils J.H. Averesch, Leonardo Castellanos, Young Hae Choi, Andreas Rothauer, Oliver Kayser

Duboisia species, which belong to the family of Solanaceae, are commercially cultivated in large scale, as they are main source of the pharmaceutically-used active compound scopolamine. In this study, 1H NMR-based metabolite profiling linking primary with secondary metabolism and additional quantification via HPCL-MS with special focus on the tropane alkaloids were applied to compare leaf and root extracts of three wild types and two hybrids of Duboisia myoporoides and D. leichhardtii at different developmental stages grown under controlled conditions in climate chambers and under agricultural field plantation. Based on the leaf extracts, a clear distinction between the Duboisia hybrids and the wild types Duboisia myoporoides and D. leichhardtii using principal component analysis of 1H NMR data was observed. The average content in scopolamine in the hybrids of Duboisia cultivated in climate chambers increased significantly from month 3–6 after potting of the rooted cuttings, however not so for the examined wild types. The Duboisia hybrids grown in climate chambers showed higher growth and contained more sugars and amino acids than Duboisia hybrids grown in the field, which in contrast showed an enhanced flux towards tropane alkaloids as well as flavonoids. For a more detailed analysis of tropane alkaloids, an appropriate HPLC-MS method was developed and validated. The measurements revealed large differences in the alkaloid pattern within the different genotypes under investigation, especially regarding the last enzymatic step, the conversion from hyoscamine to scopolamine by the hyoscyamine 6β–hydroxylase. Scopolamine was found in highest concentrations in Duboisia hybrids (20.04 ± 4.05 and 17.82 ± 3.52 mg/g dry wt) followed by Duboisia myoporoides (12.71 ± 2.55 mg/g dry wt), both showing a high selectivity for scopolamine in contrast to Duboisia leichhardtii (3.38 ± 0.59 and 5.09 ± 1.24 mg/g dry wt) with hyoscyamine being the predominant alkaloid.

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Datum: 30.09.2016


Identification and characterization of UDP-glucose:Phloretin 4′-O-glycosyltransferase from Malus x domestica Borkh

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Mosaab Yahyaa, Rachel Davidovich-Rikanati, Yoram Eyal, Alona Sheachter, Sally Marzouk, Efraim Lewinsohn, Mwafaq Ibdah

Apples (Malus x domestica Brokh.) are among the world’s most important food crops with nutritive and medicinal importance. Many of the health beneficial properties of apple fruit are suggested to be due to (poly)phenolic metabolites, including various dihydrochalcones. Although many of the genes and enzymes involved in polyphenol biosynthesis are known in many plant species, the specific reactions that lead to the biosynthesis of the sweet tasting dihydrochalcones, such as trilobatin, are unknown. To identify candidate genes for involvement in the glycosylation of dihydrochalcones, existing genome databases of the Rosaceae were screened for apple genes with significant sequence similarity to Bacillus subtilis phloretin glycosyltransferase. Herein reported is the identification and functional characterization of a Malus x domestica gene encoding phloretin-4′-O-glycosyltransferase designated MdPh-4′-OGT. Recombinant MdPh-4′-OGT protein glycosylates phloretin in the presence of UDP-glucose into trilobatin in vitro. Its apparent K m values for phloretin and UDP-glucose were 26.1 μM and 1.2 mM, respectively. Expression analysis of the MdPh-4′-OGT gene indicated that its transcript levels showed significant variation in apple tissues of different developmental stages.

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Datum: 30.09.2016


Direct evidence of specific localization of sesquiterpenes and marchantin A in oil body cells of Marchantia polymorpha L.

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): M. Tanaka, T. Esaki, H. Kenmoku, T. Koeduka, Y. Kiyoyama, T. Masujima, Y. Asakawa, K. Matsui

Liverworts are a rich source of a diverse array of specialized metabolites, such as terpenoids and benzenoids, which are potentially useful for pharmaceutical or agrochemical applications, and also provide clues to elucidate the strategy by which liverworts adapt to the terrestrial environment. Liverworts, belonging to orders Marchantiales and Jungermanniales, possess oil bodies. In Marchantia polymorpha L., oil bodies are confined to scattered idioblastic oil body cells. It has been assumed that the specialized metabolites in M. polymorpha specifically accumulate in the oil bodies in oil body cells; however, no direct evidence was previously available for this specific accumulation. In this study, direct evidence was obtained using micromanipulation techniques coupled with MS analysis that demonstrated the specific accumulation of sesquiterpenoids and marchantin A in the oil body cells of M. polymorpha thalli. It was also observed that the number of oil body cells increased in thalli grown in low-mineral conditions. The amounts of sesquiterpenoids and marchantin A detected in crude extract prepared from the whole thallus were roughly proportional to the number of oil body cells found in a given volume of thallus, suggesting that oil body cell differentiation and sesquiterpenoid and marchantin A biosynthetic pathways are coordinated with each other.

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Datum: 30.09.2016


Effect of salinity on the fatty acid and triacylglycerol composition of five haptophyte algae from the genera Coccolithophora, Isochrysis and Prymnesium determined by LC-MS/APCI

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Linda Nedbalová, Antonín Střížek, Karel Sigler, Tomáš Řezanka

Non-aqueous reversed-phase high-performance liquid chromatography (NARP-HPLC) with atmospheric pressure chemical ionization (APCI) was used for separation of triacylglycerols from five strains of haptophyte algae (genera Coccolithophora, Isochrysis, and Prymnesium). This study describes the separation and identification of C18 polyunsaturated triacylglycerols containing stearidonic and octadecapentaenoic fatty acids, including their regioisomers. Salinity affects the proportion of saturated and unsaturated fatty acids. The biosynthesis of C18 polyunsaturated triacylglycerols was found to be very stereospecific and to depend on the salinity of cultivation media, asymmetric regioisomers predominating at low salinity (sn-OpOpSt and/or PoStSt) and symmetric ones at high salinity (sn-OpStOp and or StPoSt).

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Datum: 30.09.2016


Stilbene biosynthesis in the needles of spruce Picea jezoensis

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): K.V. Kiselev, V.P. Grigorchuk, Z.V. Ogneva, A.R. Suprun, A.S. Dubrovina

Stilbenes are valuable phenolic compounds that are synthesized in plants via the phenylpropanoid pathway where stilbene synthase (STS) directly catalyzes resveratrol or pinosylvin formation. Currently, there is a lack of information about the stilbene biosynthetic pathway in spruce (Picea). Resveratrol and piceatannol derivatives have been detected in the spruce bark, needles, and roots. We analyzed seasonal variation in stilbene spectrum and content in the needles of different ages of one tree of spruce Picea jezoensis. HPLC analysis revealed the presence of nine stilbenes: t- and cis-astringin, t- and cis-piceid, t- and cis-isorhapontin, and t-piceatannol were present in amounts of 0.01–6.07 mg/g of dry weight (DW), while t-isorhapontigenin and t-resveratrol were present in traces (0.001–0.312 μg/g DW). T-astringin prevailed over other stilbenoid compounds (66–86% of all stilbenes). The highest total stilbene content was detected in one-year-old needles collected in the autumn and spring (5.4–7.77 mg/g DW). We previously cloned and sequenced full-length cDNAs of the four STS transcripts (PjSTS1a, PjSTS1b, PjSTS2, and PjSTS3) of P. jezoensis. This study presents a detailed analysis of seasonal variations in PjSTS1a, 1b, 2, and 3 transcript levels in the needles of P. jezoensis of different ages using qRT-PCR. PjSTS1a and PjSTS1b transcription was higher in the needles collected in the autumn, spring, or summer than in the winter. PjSTS2 was actively transcribed in the needles of all ages collected in the winter, spring, and summer. PjSTS3 expression did not significantly change during the year and did not depend on the age of the needles. Therefore, the data show that high levels of the stilbene glucosides and PjSTS expression are present in the needles of P. jezoensis.

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Datum: 30.09.2016


Phytohormone profile in Lactuca sativa and Brassica oleracea plants grown under Zn deficiency

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Eloy Navarro-León, Alfonso Albacete, Alejandro de la Torre-González, Juan M. Ruiz, Begoña Blasco

Phytohormones, structurally diverse compounds, are involved in multiple processes within plants, such as controlling plant growth and stress response. Zn is an essential micronutrient for plants and its deficiency causes large economic losses in crops. Therefore, the purpose of this study was to analyse the role of phytohormones in the Zn-deficiency response of two economically important species, i.e. Lactuca sativa and Brassica oleracea. For this, these two species were grown hydroponically with different Zn-application rates: 10 μM Zn as control and 0.1 μM Zn as deficiency treatment and phytohormone concentration was determined by U-HPLC-MS. Zn deficiency resulted in a substantial loss of biomass in L. sativa plants that was correlated with a decline in growth-promoting hormones such as indole-3-acetic acid (IAA), cytokinins (CKs), and gibberellins (GAs). However these hormones increased or stabilized their concentrations in B. oleracea and could help to maintain the biomass in this species. A lower concentration of stress-signaling hormones such as ethylene precursor aminocyclopropane-1-carboxylic acid (ACC), abscisic acid (ABA), salicylic acid (SA) and jasmonic acid (JA) and also CKs might be involved in Zn uptake in L. sativa while a rise in GA4, isopentenyl adenine (iP), and ACC and a fall in JA and SA might contribute to a better Zn-utilization efficiency (ZnUtE), as observed in B. oleracea plants.

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Datum: 30.09.2016


Effect of growth temperature on glucosinolate profiles in Arabidopsis thaliana accessions

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Ralph Kissen, Franziska Eberl, Per Winge, Eivind Uleberg, Inger Martinussen, Atle M. Bones

Glucosinolates are plant secondary metabolites with important roles in plant defence against pathogens and pests and are also known for their health benefits. Understanding how environmental factors affect the level and composition of glucosinolates is therefore of importance in the perspective of climate change. In this study we analysed glucosinolates in Arabidopsis thaliana accessions when grown at constant standard (21 °C), moderate (15 °C) and low (9 °C) temperatures during three generations. In most of the tested accessions moderate and pronounced chilling temperatures led to higher levels of glucosinolates, especially aliphatic glucosinolates. Which temperature yielded the highest glucosinolate levels was accession-dependent. Transcriptional profiling revealed also accession-specific gene responses, but only a limited correlation between changes in glucosinolate-related gene expression and glucosinolate levels. Different growth temperatures in one generation did not consistently affect glucosinolate composition in subsequent generations, hence a clear transgenerational effect of temperature on glucosinolates was not observed.

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Datum: 30.09.2016


Induced defenses change the chemical composition of pine seedlings and influence meal properties of the pine weevil Hylobius abietis

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Lina Lundborg, Frauke Fedderwitz, Niklas Björklund, Göran Nordlander, Anna-Karin Borg-Karlson

The defense of conifers against phytophagous insects relies to a large extent on induced chemical defenses. However, it is not clear how induced changes in chemical composition influence the meal properties of phytophagous insects (and thus damage rates). The defense can be induced experimentally with methyl jasmonate (MeJA), which is a substance that is produced naturally when a plant is attacked. Here we used MeJA to investigate how the volatile contents of Scots pine (Pinus sylvestris L.) tissues influence the meal properties of the pine weevil (Hylobius abietis (L.)). Phloem and needles (both weevil target tissues) from MeJA-treated and control seedlings were extracted by n-hexane and analyzed by two-dimensional gas chromatography-mass spectrometry (2D GC-MS). The feeding of pine weevils on MeJA-treated and control seedlings were video-recorded to determine meal properties. Multivariate statistical analyses showed that phloem and needle contents of MeJA-treated seedlings had different volatile compositions compared to control seedlings. Levels of the pine weevil attractant (+)-α-pinene were particularly high in phloem of control seedlings with feeding damage. The antifeedant substance 2-phenylethanol occurred at higher levels in the phloem of MeJA-treated than in control seedlings. Accordingly, pine weevils fed slower and had shorter meals on MeJA-seedlings. The chemical compositions of phloem and needle tissues were clearly different in control seedlings but not in the MeJA-treated seedlings. Consequently, meal durations of mixed meals, i.e. both needles and phloem, were longer than phloem meals on control seedlings, while meal durations on MeJA seedlings did not differ between these meal contents. The meal duration influences the risk of girdling and plant death. Thus our results suggest a mechanism by which MeJA treatment may protect conifer seedlings against pine weevils.

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Datum: 30.09.2016


Variation in the flavonolignan composition of fruits from different Silybum marianum chemotypes and suspension cultures derived therefrom

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Lennart Poppe, Maike Petersen

Mature fruits collected from different milk thistle (Silybum marianum (L.) Gaertn.) plants, grown in various habitats in Europe, were analysed for silymarin content and variation in component composition. Two different German and Polish cultivars each, as well as fruits from Hungary and Bulgaria have been compared with respect to their ratio of flavonolignan regioisomers. Besides differences in total silymarin content (0.8%–4.9%), three distinct chemotypical variations in fruit flavonolignan regioisomer composition in the cultivars have been observed. Although the differences in the diastereomer ratios of silybin A/B and isosilybin A/B were not significant, they never appeared in a 1:1 ratio. In vitro cultures have been established from seedlings of three typical chemotypes for further insights into flavonolignan content and composition in suspension cultures and the release of these specialized compounds to the extracellular space. The differences in the three Silybum marianum chemotypes were also observed in the composition of the intracellular silymarin of suspension-cultured cells. Silymarin components released to the cell culture medium, however, showed a highly differing composition with only low amounts of silychristin and silydianin. Assays with crude protein extracts prepared from suspension cells or habituated medium of these three chemotypes did not result in differences in silymarin content or composition. In in vitro assays the formation of the regioisomers silydianin and silychristin were strongly influenced by the taxifolin:coniferyl alcohol concentration ratio.

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Datum: 30.09.2016


Evolutionary correlations in flavonoid production across flowers and leaves in the Iochrominae (Solanaceae)

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Andrea E. Berardi, Sherry B. Hildreth, Richard F. Helm, Brenda S.J. Winkel, Stacey D. Smith

Plant reproductive and vegetative tissues often use the same biochemical pathways to produce specialized metabolites. In such cases, selection acting on the synthesis of specific products in a particular tissue could result in correlated changes in other products of the pathway, both in the same tissue and in other tissues. This study examined how changes in floral anthocyanin pigmentation affect the production of other compounds of the flavonoid pathway in flowers and in leaves. Focusing on the Iochrominae, a clade of Solanaceae with a wide range of flower colors, liquid chromatography coupled with mass spectrometry and UV detection was used to profile and quantify the variation in two classes of flavonoids, anthocyanins and flavonols. Purple, red, orange and white-flowered Iochrominae produced all of the six common anthocyanidin types, as well as several classes of flavonols. Differences in anthocyanin and flavonol production were significantly correlated in flowers, particularly with respect to B ring hydroxylation pattern. However, these differences in floral flavonoids were not strongly related to differences in leaf chemistry. Specifically, most species made only flavonols (not anthocyanins) in leaves, and these comprised the two most common flavonols, quercetin and kaempferol, regardless of the color of the flower. These results suggest that shifts in flower color may occur without significant pleiotropic consequences for flavonoid production in vegetative tissues. Similar studies in other systems will be important for testing the generality of this pattern in other groups of flowering plants.

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Datum: 30.09.2016


Abietane-type diterpenoids from the roots of Caryopteris mongolica and their cholinesterase inhibitory activities

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Toshihiro Murata, Yoshinobu Ishikawa, Erdenebileg Saruul, Erdenechimeg Selenge, Kenroh Sasaki, Kaoru Umehara, Fumihiko Yoshizaki, Javzan Batkhuu

Eleven abietane-type diterpenoids and two known abietanes were isolated from the roots of Caryopteris mongolica, and their structures were characterized. The absolute configurations at C-5 and C-10 were determined from the NMR data, including from the nuclear Overhauser effect and CD spectra, and the absolute configuration of C-16 in the hydroxypropyl group was determined via a modified Mosher’s method. Furthermore, the previously unknown absolute configuration of the C-15 of cyrtophyllone B was determined to be in an R-configuration using X-ray crystallography. To estimate the preventive effects of the isolates for neurodegenerative disease development, their inhibitory activities against acetylcholinesterase (AChE) from human erythrocytes and butyrylcholinesterase (BChE) from horse serum were evaluated.

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Datum: 30.09.2016


Naphthohydroquinones, naphthoquinones, anthraquinones, and a naphthohydroquinone dimer isolated from the aerial parts of Morinda parvifolia and their cytotoxic effects through up-regulation of p53

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Jie Kang, Peng Zhang, Zengping Gao, Jian Zhang, Zheng Yan, Hongqing Wang, Ruoyun Chen

Five unknown compounds, morindaparvins C–G, consisting of naphthohydroquinones, a naphthoquinone, an anthraquinone, and a naphthohydroquinone dimer, together with three known quinones and seven other known compounds, were isolated from the aerial parts of Morinda parvifolia. The structures of morindaparvins C, D, E, F, and G were elucidated on the basis of spectroscopic or X-ray diffraction analysis as methyl 4-hydroxy-1,6-dimethoxy-naphthalene-2-carboxylate, methyl 4,8-dihydroxy-1-methoxy-naphthalene-2-carboxylate, 3-amino-6-methoxy-2-methoxycarbonyl-1,4-naphthoquinone, 1,4-dihydroxy-7-hydroxymethyl-anthraquinone, and dimethyl 1,1′-dihydroxy-4,4′,7,7′-tetramethoxy-2,2′-binaphthalene-3,3′-dicarboxylate, respectively. Naphthoquinones and naphthohydroquinone dimers were previously unknown in the genus Morinda. In addition, the compounds were tested for cytotoxicity against four human cancer cell lines HeLa, A2780, Ketr3 and MCF-7 and their effects on p53-activated transcription. Three naphthoquinones had moderate cytotoxic effects with IC50 values ranging from 1.51 to 9.56 μM, through up-regulation of p53 transcriptional activity.

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Datum: 30.09.2016


Homologous and heterologous expression of grapevine E-(β)-caryophyllene synthase (VvGwECar2)

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Umberto Salvagnin, Silvia Carlin, Sergio Angeli, Urska Vrhovsek, Gianfranco Anfora, Mickael Malnoy, Stefan Martens

E-(β)-caryophyllene is a sesquiterpene volatile emitted by plants and involved in many ecological interactions within and among trophic levels and it has a kairomonal activity for many insect species. In grapevine it is a key compound for host-plant recognition by the European grapevine moth, Lobesia botrana, together with other two sesquiterpenes. In grapevine E-(β)-caryophyllene synthase is coded by the VvGwECar2 gene, although complete characterization of the corresponding protein has not yet been achieved. Here we performed the characterization of the enzyme after heterologous expression in E. coli, which resulted to produce in vitro also minor amounts of the isomer α-humulene and of germacrene D. The pH optimum was estimated to be 7.8, and the Km and Kcat values for farnesyl pyrophosphate were 31.4 μM and 0.19 s−1 respectively. Then, we overexpressed the gene in the cytoplasm of two plant species, Arabidopsis thaliana and the native host Vitis vinifera. In Arabidopsis the enzyme changed the plant head space release, showing a higher selectivity for E-(β)-caryophyllene, but also the production of thujopsene instead of germacrene D. Overall plants increased the E-(β)-caryophyllene emission in the headspace collection by 8-fold compared to Col-0 control plants. In grapevine VvGwECar2 overexpression resulted in higher E-(β)-caryophyllene emissions, although there was no clear correlation between gene activity and sesquiterpene quantity, suggesting a key role by the plant regulation machinery.

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Datum: 30.09.2016


Quantitative analysis of glycerol in dicarboxylic acid-rich cutins provides insights into Arabidopsis cutin structure

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Weili Yang, Mike Pollard, Yonghua Li-Beisson, John Ohlrogge

Cutin is an extracellular lipid polymer that contributes to protective cuticle barrier functions against biotic and abiotic stresses in land plants. Glycerol has been reported as a component of cutin, contributing up to 14% by weight of total released monomers. Previous studies using partial hydrolysis of cuticle-enriched preparations established the presence of oligomers with glycerol-aliphatic ester links. Furthermore, glycerol-3-phosphate 2-O-acyltransferases (sn-2-GPATs) are essential for cutin biosynthesis. However, precise roles of glycerol in cutin assembly and structure remain uncertain. Here, a stable isotope-dilution assay was developed for the quantitative analysis of glycerol by GC/MS of triacetin with simultaneous determination of aliphatic monomers. To provide clues about the role of glycerol in dicarboxylic acid (DCA)-rich cutins, this methodology was applied to compare wild-type (WT) Arabidopsis cutin with a series of mutants that are defective in cutin synthesis. The molar ratio of glycerol to total DCAs in WT cutins was 2:1. Even when allowing for a small additional contribution from hydroxy fatty acids, this is a substantially higher glycerol to aliphatic monomer ratio than previously reported for any cutin. Glycerol content was strongly reduced in both stem and leaf cutin from all Arabidopsis mutants analyzed (gpat4/gpat8, att1-2 and lacs2-3). In addition, the molar reduction of glycerol was proportional to the molar reduction of total DCAs. These results suggest “glycerol-DCA-glycerol” may be the dominant motif in DCA-rich cutins. The ramifications and caveats for this hypothesis are presented.

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Datum: 30.09.2016


Officimalonic acids A−H, lanostane triterpenes from the fruiting bodies of Fomes officinalis

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Jianxin Han, Liya Li, Jialiang Zhong, Zeynep Tohtaton, Qing Ren, Li Han, Xueshi Huang, Tao Yuan

Phytochemical investigation of the methanolic extract of the fruiting bodies of Fomes officinalis led to the isolation of eight 24-methyl-lanostane triterpenes named officimalonic acids A−H, along with one known lanostane triterpene. Their structures were elucidated based on the analysis of spectroscopic data, single-crystal X-ray diffraction, and electronic circular dichroism. Officimalonic acid A represents a previously unknown triterpene type with a 24-methyl-7(8 → 9)abeo-lanostane skeleton, and all of the compounds possessed a malonate half-ester moiety at C-3. Anti-inflammatory assay revealed that officimalonic acids D, E, G, H, and fomitopsin A showed potent inhibitory effects (IC50 = 5.1–8.9 μM) on nitric oxide production in lipopolysaccharide-induced RAW264.7 cells. Officimalonic acids E, G, H showed moderate cytotoxicity against H460, HepG2 and BGC-823 human cell lines.

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Datum: 30.09.2016


Composition of cuticular waxes coating flag leaf blades and peduncles of Triticum aestivum cv. Bethlehem

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Radu C. Racovita, Shelly Hen-Avivi, Josefina-Patricia Fernandez-Moreno, Antonio Granell, Asaph Aharoni, Reinhard Jetter

The work herein presents comprehensive analyses of the cuticular wax mixtures covering the flag leaf blade and peduncle of bread wheat (Triticum aestivum) cv. Bethlehem. Overall, Gas Chromatography-Mass Spectrometry and Flame Ionization Detection revealed a wax coverage of flag leaf blades (16 μg/cm2) a third that of peduncles (49 μg/cm2). Flag leaf blade wax was dominated by 1-alkanols, while peduncle wax contained primarily β-diketone and hydroxy-β-diketones, thus suggesting differential regulation of the acyl reduction and β-diketone biosynthetic pathways in the two analyzed organs. The characteristic chain length distributions of the various wax compound classes are discussed in light of their individual biosynthetic pathways and biosynthetic relationships between classes. Along with previously reported wheat wax compound classes (fatty acids, 1-alkanols, 1-alkanol esters, aldehydes, alkanes, β-diketone, hydroxy-β-diketones, alkylresorcinols and methyl alkylresorcinols), esters of 2-alkanols and three types of aromatic esters (benzyl, phenethyl and p-hydroxyphenethyl) are also reported. In particular, 2-heptanol esters were identified. Detailed analyses of the isomer distributions within 1-alkanol and 2-alkanol ester homologs revealed distinct patterns of esterified acids and alcohols, suggesting several wax ester synthases with very different substrate preferences in both wheat organs. Terpenoids, including two terpenoid esters, were present only in peduncle wax.

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Datum: 30.09.2016


The natural plant stress elicitor cis-jasmone causes cultivar-dependent reduction in growth of the stink bug, Euschistus heros and associated changes in flavonoid concentrations in soybean, Glycine max

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): José P. da Graça, Tatiana E. Ueda, Tatiani Janegitz, Simone S. Vieira, Mariana C. Salvador, Maria C.N. de Oliveira, Sonia M. Zingaretti, Stephen J. Powers, John A. Pickett, Michael A. Birkett, Clara B. Hoffmann-Campo

To test the hypothesis that the plant stress related elicitor cis-jasmone (cJ) provides protection in soybean pods against the seed-sucking stink bug pest, Euschistus heros, the growth of E. heros on cJ-treated pods was investigated using three soybean cultivars differing in insect susceptibility, i.e. BRS 134 (susceptible), IAC 100 (resistant) and Dowling (resistant). E. heros showed reduced weight gain when fed cJ-treated Dowling, whereas no effect on weight gain was observed when fed other treated cultivars. Using analysis of variance, a three factor (cultivar x treatment x time) interaction was observed with concentrations of the flavonoid glycosides daidzin and genistin, and their corresponding aglycones, daidzein and genistein. There were increases in genistein and genistin concentrations in cJ-treated Dowling at 144 and 120 h post treatment, respectively. Higher concentrations of malonyldaidzin and malonylgenistin in Dowling, compared to BRS 134 and IAC 100, were observed independently of time, the highest concentrations being observed in cJ-treated seeds. Levels of glycitin and malonylglycitin were higher in BRS 134 and IAC 100 compared to Dowling. Canonical variate analysis indicated daidzein (in the first two canonical variates) and genistein (in the first only) as important discriminatory variables. These results suggest that cJ treatment leads to an increase in the levels of potentially defensive isoflavonoids in immature soybean seeds, but the negative effect upon E. heros performance is cultivar-dependent.

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Datum: 30.09.2016


Mass spectrometric imaging of flavonoid glycosides and biflavonoids in Ginkgo biloba L.

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Sebastian Beck, Julia Stengel

Ginkgo biloba L. is known to be rich in flavonoids and flavonoid glycosides. However, the distribution within specific plant organs (e.g. within leaves) is not known. By using HPLC-MS and MS/MS we have identified a number of previously known G. biloba flavonoid glycosides and biflavonoids from leaves. Namely, kaempferol, quercetin, isorhamnetin, myricetin, laricitrin/mearnsetin and apigenin glycosides were identified. Furthermore, biflavonoids like ginkgetin/isoginkgetin were also detected. The application of MALDI mass spectrometric imaging, enabled the compilation of concentration profiles of flavonoid glycosides and biflavonoids in G. biloba L. leaves. Both, flavonoid glycosides and biflavonoids show a distinct distribution in leaf thin sections of G. biloba L.

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Datum: 30.09.2016


Cytotoxic triterpenoid saponins from Clematis tangutica

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Min Zhao, Zhuo-Ma Da-Wa, Da-Le Guo, Dong-Mei Fang, Xiao-Zhen Chen, Hong-Xi Xu, Yu-Cheng Gu, Bing Xia, Lei Chen, Li-Sheng Ding, Yan Zhou

Eight previously undescribed oleanane-type triterpenoid saponins, clematangoticosides A-H, together with eight known saponins, were isolated from the whole plants of Clematis tangutica (Maxim.) Korsh. Their structures were elucidated by extensive spectroscopic analysis, in combination with chemical methods (acid hydrolysis and mild alkaline hydrolysis). Clematangoticosides D-G were found to be unusual 23, 28-bidesmosidic glycosides. The cytotoxic activities of all of the isolated saponins were evaluated against the four human cancer cell lines SGC-7901, HepG2, HL-60 and U251MG. Clematoside S, sapindoside B, kalopanax saponin A, and koelreuteria saponin A exhibited cytotoxicity against all of the test cancer cell lines with IC50 values in the range of 1.88–27.20 μM, while clematangoticoside D and F showed selective cytotoxicity against SGC-7901 with IC50 values of 24.22 and 21.35 μM, respectively.

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Datum: 30.09.2016


Natural variability in acyl moieties of sugar esters produced by certain tobacco and other Solanaceae species

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Antoaneta B.M. Kroumova, Dave Zaitlin, George J. Wagner

A unique feature of glandular trichomes of plants in the botanical family Solanaceae is that they produce sugar esters (SE), chemicals that have been shown to possess insecticidal, antifungal, and antibacterial properties. Sugar esters of tobacco (Nicotiana tabacum) provide pest resistance, and are important flavor precursors in oriental tobacco cultivars. Acyl moieties of SEs in Nicotiana spp., petunia, and tomato are shown to vary with respect to carbon length and isomer structure (2–12 carbon chain length; anteiso-, iso-, and straight-chain). Sugar esters and their acyl groups could serve as a model to explore the basis of phenotypic diversity and adaptation to natural and agricultural environments. However, information on the diversity of acyl composition among species, cultivars, and accessions is lacking. Herein, described is the analysis of SE acyl groups found in 21 accessions of Nicotiana obtusifolia (desert tobacco), six of Nicotiana occidentalis subsp. hesperis, three of Nicotiana alata, two of N. occidentalis, four modern tobacco cultivars, five petunia hybrids, and one accession each of a primitive potato (Solanum berthaultii) and tomato (Solanum pennellii). A total of 20 different acyl groups was observed that were represented differently among cultivars, species, and accessions. In Nicotiana species, acetate and iso- and anteiso-branched acids prevailed. Straight-chain groups (2–8 carbons) were prominent in petunias, while octanoic acid was prominent in N. alata and N. × sanderae. Two unexpected acyl groups, 8-methyl nonanoate and decanoate were found in N. occidentalis subsp. hesperis. Longer chain groups were found in the petunia, tomato, and potato species studied.

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Datum: 30.09.2016


Arbuscular mycorrhizal symbiosis stimulates key genes of the phenylpropanoid biosynthesis and stilbenoid production in grapevine leaves in response to downy mildew and grey mould infection

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Sébastien Bruisson, Pascale Maillot, Paul Schellenbaum, Bernard Walter, Katia Gindro, Laurence Deglène-Benbrahim

Grapevine (Vitis spp) is susceptible to serious fungal diseases usually controlled by chemical treatments. Arbuscular mycorrhizal fungi (AMF) are obligate plant symbionts which can stimulate plant defences. We investigated the effect of mycorrhization on grapevine stilbenoid defences. Vitis vinifera cvs Chasselas, Pinot noir and the interspecific hybrid Divico, on the rootstock 41B, were mycorrhized with Rhizophagus irregularis before leaf infection by Plasmopara viticola or Botrytis cinerea. Gene expression analysis showed an up-regulation of PAL, STS, and ROMT, involved in the stilbenoid biosynthesis pathway, in plant leaves, 48 h after pathogen inoculation. This defense response could be potentiated under AMF colonization, with an intensity level depending on the gene, the plant cultivar and/or the pathogen. We also showed that higher amounts of active forms of stilbenoids (i.e trans-form of resveratrol, ε- and δ-viniferins and pterostilbene) were produced in mycorrhized plants of the three genotypes in comparison with non-mycorrhized ones, 10 days post-inoculation with either pathogen. These results support the hypothesis that AMF root colonization enhances defence reactions against a biotrophic and a necrotrophic pathogen, in the aerial parts of grapevine.

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Datum: 30.09.2016


Hepatoprotective pyranocoumarins from the stems of Clausena emarginata

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Hong-Min Xia, Chuang-Jun Li, Jing-Zhi Yang, Jie Ma, Yan Li, Li Li, Dong-Ming Zhang

Seven pyranocoumarins, clauemarmarins A−G, along with 6 known analogues were isolated from the stems of Clausena emarginata. Their structures were elucidated by extensive spectroscopic analyses, and the absolute stereochemistries at C-6″ of clauemarmarin B, C and D and the absolute configurations of clauemarmarin E, F and G were determined by ECD experiments. Compounds clauemarmarin C, D and two known analogues exhibited hepatoprotective activities against DL-galactosamine-induced damage in WB-F344 cells at the concentration of 10 μM.

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Datum: 30.09.2016


Zebiriosides A-L, oleanane saponins from the roots of Dendrobangia boliviana

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Ilhem Zebiri, Mohamed Haddad, Laurent Duca, Dominique Harakat, Billy Cabanillas, Lucie Paloque, Amandine Scandolera, Michel Sauvain, Elsa Rengifo, Laurence Voutquenne-Nazabadioko

Twelve oleanane saponins, zebiriosides A-L, were isolated from the roots of Dendrobangia boliviana Rusby, together with two known saponins, talunùmoside I and 3-O-β-d-glucuronopyranosyl serjanic acid. These saponins are glycosides of serjanic or phytolaccinic acid. Their structures were established on two basis: first, their spectral data, mainly HR-TOFESIMS, 1D-NMR (1H, 13C, DEPT) and 2D-NMR (1H 1H COSY, TOCSY, HSQC, HMBC, and ROESY), and second by comparison with literature data. These compounds were evaluated for their cytotoxic, antileishmanial and hemolytic activities. No antileishmanial or hemolytic activities were revealed, however zebirioside C and zebirioside I showed cytotoxicity against fibroblasts with IC50 of 6.4 and 5.6 μM, respectively.

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Datum: 30.09.2016


Composition of the epicuticular waxes coating the adaxial side of Phyllostachys aurea leaves: Identification of very-long-chain primary amides

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Radu C. Racovita, Reinhard Jetter

The present study presents comprehensive chemical analyses of cuticular wax mixtures of the bamboo Phyllostachys aurea. The epicuticular and intracuticular waxes were sampled selectively from the adaxial side of leaves on young and old plants and investigated by gas chromatography-mass spectrometry and flame ionization detection. The epi- and intracuticular layers on young and old leaves had wax loads ranging from 1.7 μg/cm2 to 1.9 μg/cm2. Typical very-long-chain aliphatic wax constituents were found with characteristic chain length patterns, including alkyl esters (primarily C48), alkanes (primarily C29), fatty acids (primarily C28 and C16), primary alcohols (primarily C28) and aldehydes (primarily C30). Alicyclic wax components were identified as tocopherols and triterpenoids, including substantial amounts of triterpenoid esters. Alkyl esters, alkanes, fatty acids and aldehydes were found in greater amounts in the epicuticular layer, while primary alcohols and most terpenoids accumulated more in the intracuticular wax. Alkyl esters occurred as mixtures of metamers, combining C20 alcohol with various acids into shorter ester homologs (C36 C40), and a wide range of alcohols with C22 and C24 acids into longer esters (C42 C52). Primary amides were identified, with a characteristic chain length profile peaking at C30. The amides were present exclusively in the epicuticular layer and thus at or near the surface, where they may affect plant-herbivore or plant-pathogen interactions.

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Datum: 30.09.2016


Chemotaxonomic perspectives of the Paracaryum (Cynoglosseae, Boraginaceae) taxa based on fruit fatty acid composition

Publication date: November 2016
Source:Phytochemistry, Volume 131

Author(s): Aslı Doğru-Koca, Tamer Özcan, Şinasi Yıldırımlı

Paracaryum is a medium sized genus in Cynoglosseae. This study represents the most comprehensive phytochemical investigation of Paracaryum to date. The fatty acid compositions of the fruits of ten Paracaryum taxa belonging to three different subgenera were investigated for chemotaxonomic allocation using gas chromatography. The fatty acid profiles of seven Paracaryum taxa, five of which are endemic to Turkey, were recorded for the first time. Among the twenty-two analysed fatty acids, oleic, linoleic and α-linolenic acids were the major fatty acids represented. The oleic acid content ranged from 22.1% in P. hirsutum to 51.7% in P. lithospermifolium subsp. cariense var. erectum; linolenic acid content ranged from 8.6% in P. lithospermifolium subsp. cariense var. erectum to 20.7% in P. erysimifolium; α-linolenic acid content ranged from 7.5% in P. lithospermifolium subsp. cariense var. erectum to 13.5% in P. cristatum subsp. cristatum; gamma linolenic acid content ranged from 2.8% in P. erysimifolium to 6.0% in P. hirsutum. Additional fatty acids also displayed varying levels in different species; palmitic acid content accounted for 17.7% in P. erysimifolium, erucic acid content was 8.73% in P. strictum, eicosenoic acid content was 6.0% in P. cristatum subsp. cristatum, eicosadienoic acid content was 4.4% in P. hirsutum, and stearic acid content was 4.3% in P. erysimifolium. The classification of the tribe Cynoglosseae remains controversial despite the many intensive morphological and phylogenetic investigations that have been carried out. Our fatty acid data from Paracaryum were analysed together with previously recorded fatty acid data from Cynoglosseae s.l. taxa to examine the chemotaxonomic contribution to the classification among taxa in Cynoglosseae by multivariate methods, including the unweighted pair group method with arithmetic mean and principal component analysis. An assessment of these chemometrics data supported the chemotaxonomic position of the genus Paracaryum in the tribe Cynoglosseae. While the principal component graphic did not depict clear separation of the three subgenera of Paracaryum, the principal component analysis revealed the chemotaxonomic significance of palmitic, linoleic, capric, and oleic acids.

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Datum: 30.09.2016


Quali-quantitative analysis of the phenolic fraction of the flowers of Corylus avellana, source of the Italian PGI product “Nocciola di Giffoni”: Isolation of antioxidant diarylheptanoids

Publication date: October 2016
Source:Phytochemistry, Volume 130

Author(s): Milena Masullo, Angela Mari, Antonietta Cerulli, Alfredo Bottone, Bogdan Kontek, Beata Olas, Cosimo Pizza, Sonia Piacente

There is only limited information available on the chemical composition of the non-edible parts of Corylus avellana, source of the Italian PGI product “Nocciola di Giffoni” (hazelnut). An initial LC-MS profile of the methanolic extract of the male flowers of C. avellana, cultivar ‘Tonda di Giffoni’ led to the isolation of 12 compounds, of which the structures were elucidated by NMR spectroscopy. These were identified as three previously undescribed diarylheptanoids, named giffonins Q-S, along with nine known compounds. Furthermore, the quantitative determination of the main compounds occurring in the methanolic extract of C. avellana flowers was carried out by an analytical approach based on LC-ESI(QqQ)MS, using the Multiple Reaction Monitoring (MRM) experiment. In order to explore the antioxidant ability of C. avellana flowers, the methanolic extract and the isolated compounds were evaluated for their inhibitory effects on human plasma lipid peroxidation induced by H2O2 and H2O2/Fe2+, by measuring the concentration of TBARS.

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Datum: 30.09.2016






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