Neoflavanoids of Dalbergia cultrata

In addition to the known neoflavanoids (S)-4-methoxydalbergione, dalbergin, and stevenin, the heartwood of Dalbergia cultrata Grah. contains a new 3,3-diphenylprop-l-ene (Ia). The assigned structure is based on data acquired mainly by physical methods. The softwood of D. ferruginea Roxb. ¹ yielded sitosterol and friedelin.     

Distribution of exudate flavonoids in the genus Plectranthus

Thirty-four species of the genus Plectranthus (including species of the former genera Coleus and Solenostemon, fam. Lamiaceae) were surveyed for exudate flavonoids to see whether the distribution of these compounds would support a recent classification of the genus based on molecular and morphological characters. In this classification two major groups had been identified, the Coleus and Plectranthus clades. Only about 40% of the species, predominantly from the Plectranthus clade, were found to produce exudate flavonoids, which were mainly flavones. Flavanones were restricted to five species of the Plectranthus clade, whereas flavonols were only found in two species of the Coleus clade, Plectranthus montanus Benth. (synonyms Plectranthus marrubioides Hochst. ex Benth. and Plectranthus cylindraceus Hochst. ex Benth.) and Plectranthus pseudomarrubioides R.H.Willemse. Four of these flavonols were isolated from P. montanus and identified by NMR spectroscopy as the 3,7-dimethyl ether and 3,7,4′-trimethyl ether of quercetin and the 3,6,7-trimethyl ether and 3,6,7,4′-tetramethyl ether of quercetagetin. The remaining flavonols and flavones were identified by HPLC–UV and LC–MS of crude extracts on the basis of their UV and mass spectra, retention times and comparison with standards. Most flavonols were 3-methyl ethers and many of the flavones and flavonols were oxygenated at the 6-position. The most common flavones, occurring in both clades, were cirsimaritin and salvigenin, which are methoxylated at the 6- and 7-positions. 6-Hydroxylated flavones such as scutellarein and ladanein were restricted to species of the Plectranthus clade.     

Fine-scale spatial genetic structure of Dalbergia nigra (Fabaceae), a threatened and endemic tree of the Brazilian Atlantic Forest

The Atlantic Forest is one of the most diverse ecosystems in the world and considered a hotspot of biodiversity conservation. Dalbergia nigra (Fabaceae) is a tree endemic to the Brazilian Atlantic Forest, and has become threatened due to overexploitation of its valuable timber. In the present study, we analyzed the genetic diversity and fine-scale spatial genetic structure of D. nigra in an area of primary forest of a large reserve. All adult individuals (N = 112) were sampled in a 9.3 ha plot, and genotyped for microsatellite loci. Our results indicated high diversity with a mean of 8.6 alleles per locus, and expected heterozygosity equal to 0.74. The co-ancestry coefficients were significant for distances among trees up to 80 m. The Sp value was equal to 0.017 and indirect estimates of gene dispersal distances ranged from 89 to 144 m. No strong evidence of bottleneck or effects of human-disturbance was found. This study highlights that long-term efforts to protect a large area of Atlantic Forest have been effective towards maintaining the genetic diversity of D. nigra. The results of this study are important towards providing a guide for seed collection for ex-situ conservation and reforestation programmes of this threatened species.     

Fabacyl acetate, a germination stimulant for root parasitic plants from Pisum sativum

A germination stimulant, fabacyl acetate, was purified from root exudates of pea (Pisum sativum L.) and its structure was determined as ent-2′-epi-4a,8a-epoxyorobanchyl acetate [(3aR,4R,4aR,8bS,E)-4a,8a-epoxy-8,8-dimethyl-3-(((R)-4-methyl-5-oxo-2,5-dihydrofuran-2-yloxy)methylene)-2-oxo-3,3a,4,5,6,7,8,8b-decahydro-2H-indeno[1,2-b]furan-4-yl acetate], by 1D and 2D NMR spectroscopic, ESI- and EI-MS spectrometric, X-ray crystallographic analyses, and by comparing the ¹H NMR spectroscopic data and relative retention times (RR_t) in LC-MS and GC-MS with those of synthetic standards prepared from (+)-orobanchol and (+)-2′-epiorobanchol. The ¹H NMR spectroscopic data and RR_t of fabacyl acetate were identical with those of an isomer prepared from (+)-2′-epiorobanchol except for the opposite sign in CD spectra. This is the first natural ent-strigolactone containing an epoxide group. Fabacyl acetate was previously detected in root exudates of other Fabaceae plants including faba bean (Vicia faba L.) and alfalfa (Medicago sativa L.).     

Coelobillardin,an iridoid glucoside dimer from Coelospermum billardieri

An isoflavanoid (6-->2) neoflavonoid dimer and a 4',5',7-trihydroxy-2'-methoxyisoflavone, both as the acetate derivatives were isolated from the heartwood of Dalbergia nitidula. Their structures were established by spectroscopic methods.     

Neocandenatone, an isoflavan-cinnamylphenol quinone methide pigment from Dalbergia congestiflora

A purple pigment neocandenatone (vestitol[6-->9";7O-->7"]obtusaquinone) was isolated from the heartwood of campincerán (Dalbergia congestiflora), an endemic Mexican tree. The isoflavan-cinnamyl phenol quinone methide structure of this compound was elucidated by HRMS, IR, and 1H and 13C NMR spectroscopic analysis, including 2D experiments (COSY, NOESY, HMQC and HSQC).     

Selective disruption of wheat secondary metabolism by herbicide safeners

In wheat (Triticum aestivum L.), treatment with herbicide safeners enhances the expression of enzymes involved in pesticide detoxification and reduces crop sensitivity to herbicides. Since these same enzymes are involved in plant secondary metabolism, it was of interest to determine whether or not the safener cloquintocet mexyl perturbed phenolic metabolism in wheat seedlings. LC/ESI/MS analysis identified 14 phenolic substrates in the shoots of young wheat plants. Fragmentation imposed by collision induced dissociation identified specific C-glycosidic conjugates of 4′,5,7-trihydroxflavone (apigenin), 3′,4′,5,7-tetrahydroxyflavone (luteolin) and 3′-O-methylluteolin. Treatment of 7-day-old wheat shoots with cloquintocet mexyl resulted in an accelerated depletion of the conjugates of all three flavones, most notably with the glycosides of luteolin. In contrast, safener treatment caused the selective accumulation of 4′,5,7-trihydroxy-3′,5′-dimethoxyflavone (tricin) and the phenylpropanoid ferulic acid. Changes in phenolic content were associated with an increase in O-methyltransferase and C-glucosyltransferase activity toward flavonoid substrates as well as the classic enhancement of detoxifying glutathione transferases. Our results suggest that in addition to altering the capacity of wheat to metabolise herbicides and other xenobiotics, safeners can also cause a selective shift in the metabolism of endogenous phenolics.     

Phylogeography of the endangered rosewood Dalbergia nigra (Fabaceae): insights into the evolutionary history and conservation of the Brazilian Atlantic Forest

The Brazilian rosewood (Dalbergia nigra) is an endangered tree endemic to the central Brazilian Atlantic Forest, one of the world''s most threatened biomes. The population diversity, phylogeographic structure and demographic history of this species were investigated using the variation in the chloroplast DNA (cpDNA) sequences of 185 individuals from 19 populations along the geographical range of the species. Fifteen haplotypes were detected in the analysis of 1297 bp from two non-coding sequences, trnV-trnM and trnL. We identified a strong genetic structure (F_ST=0.62, P<0.0001), with a latitudinal separation into three phylogeographic groups. The two northernmost groups showed evidence of having maintained historically larger populations than the southernmost group. Estimates of divergence times between these groups pointed to vicariance events in the Middle Pleistocene (ca. 350 000–780 000 years ago). The recurrence of past climatic changes in the central part of the Atlantic forest, with cycles of forest expansion and contraction, may have led to repeated vicariance events, resulting in the genetic differentiation of these groups. Based on comparisons among the populations of large reserves and small, disturbed fragments of the same phylogeographic group, we also found evidence of recent anthropogenic effects on genetic diversity. The results were also analysed with the aim of contributing to the conservation of D. nigra. We suggest that the three phylogeographic groups could be considered as three distinct management units. Based on the genetic diversity and uniqueness of the populations, we also indicate priority areas for conservation.     

Dalbergia prazeri Prain(豆科)之考证

在发表Dalbergia prazeri Prain时Prain曾认为其与托叶黄檀(D.stipulacea Roxb.)近缘,只是该种小叶背面疏被微柔毛,花萼被硬毛与托叶黄檀不同,同时又指出其荚果也与后者不同,但是并没有解释其不同点。之后Prain又将其归并入奥氏黄檀(D.oliveri Gamble ex Prain),亦未给出相应的理由。经研究D.prazeri Prain与南岭黄檀(D.assamica Benth.)为同种,而被归并入后者。Prain发表该种时引证Prazer s.n.为模式,但并没有指定主模式。涉及该种的Prazer s.n.的标本共有6份,该文将藏于印度国立标本馆加尔各答馆(CAL),条形码为CAL0000012326(CAL标本号131311)的标本指定为后选模式(lectotype),其余分别藏于加尔各答标本馆的4份及英国皇家植物园邱园标本馆(K)的1份为等后选模式(isolectotype)。     

红果黄檀—新异名

在比较研究标本馆标本的基础上,确认Dalbergia darlacensis P.H.H(o)& Niyomdham与红果黄檀(D.tsoi Merr.et Chun)为同种植物,并把前者作为后者的异名处理.     

Pterocarpans from Dalbergia spruceana

The wood of Dalbergia spruceana contains, besides O-acetyloleanolic acid, elemicin and 3,4,5-trimethoxy-cinnamaldehyde; the neoflavonoids (S)-4-methoxydalbergione and dalbergin; the isoflavones biochanin-A, formononetin, pseudobaptigenin and caviunin; and the pterocarpans (±)-medicarpin, (±)-maackiain, as well as the 3,4-dihydroxy-, 3-hydroxy-4-methoxy- and 4-hydroxy-3-methoxy-derivatives of (6aR,11aR)-8,9-methylenedioxypterocarpan. The constitutions of the three last named compounds were deduced by spectra and confirmed by synthesis of (±)-4-hydroxy-3-methoxy-8,9-methylenedioxypterocarpan.     

ent-Eudesmane sesquiterpenoids, galloyl esters of the oak lactone precursor, and a 3-O-methylellagic acid glycoside from the wood of Platycarya strobilacea

ent-Eudesmane sesquiterpenoids, 8,11-dihydroxy-2,4-cycloeudesmane, 11-hydroxy-2,4-cycloeudesman-8-one and 2,4-cyclo-7(11)-eudesmen-8-one, were isolated from the wood of Platycarya strobilacea, which has been used as an aromatic tree since at least the 18th century. On charring the wood, 2,4-cyclo-7(11)-eudesmen-8-one was detected in the smoke. In the charred wood, the concentrations of ellagitannins, such as galloyl pedunculagin, dramatically decreased, whereas concentrations of pentagalloyl glucose, and other gallotannins were relatively stable. In addition, two other compounds, the 6′-O-m- and p-digalloyl oak lactone precursor and the 3-O-methylellagic acid 4′-O-(4″-O-galloyl)-xylopyranoside, were isolated from the charred wood along with m- and p-digallic acid.     

Natural Product Antifoulants from the octocorals of Indian waters

Natural Product Antifoulants (NPAs) have been proposed as one of the best alternatives for the globally banned toxic biocide -TBT-in antifouling coatings. In search of NPAs from Indian waters twenty nine species of Octocorals, collected from Gulf of Mannar and Lakshadweep islands, were screened for their antifouling potential against the cyprids of the cosmopolitan biofouler, Balanus amphitrite. The crude extracts of 8 species of these corals (Cladiella krempfi, Lobophytum irregulare, Lobophytum sarcophytoides, Sarcophyton ehrenbergi, Sarcophyton glaucum, Sinularia kavarattiensis, Melitodes sp. and Subergorgia reticulata) exhibited relatively high settlement inhibition properties. The bioassay-guided purification of the crude extracts of 3 active and abundant species-Cladiella krempfi, Sinularia kavarattiensis and Subergorgia reticulata-yielded five NPAs, (l’E,5′E)-2-(2′,6′-dimethylocta-l’,5′,7′-trienyl)-4-furoic acid 1, (−)-6-??-hydroxy polyanthellin A 2, (+)-(7R,10S)-2-methoxy calamenene 3, (+)-(7R,10S)-2,5-dimethoxy calamenene 4 and (+)-(7R,10S)-2-methoxy,5-acetoxy calamenene 5). Among these, 5 exhibited high future prospects on account of its low EC₅₀ value (0.0335 ??g/ml) and high therapeutic ratio (799).     

两粤黄檀乙醇提取物化学成分分析及抗炎活性研究

为了研究壮药两粤黄檀的化学成分及其抗炎活性,阐明其药理作用机制,该研究采用小鼠二甲苯致炎耳廓肿胀法、角叉菜胶致炎足肿胀急性炎症模型,观察不同剂量两粤黄檀乙醇提取物对小鼠耳廓肿胀度、肿胀率及足肿胀度的影响,并利用液相色谱-质谱(LC-MS)、热裂解气相色谱-质谱(PY-GC/MS)等技术分析提取物的化学成分,结合网络药理...     

Phytotoxic polyacetylenes from roots of Russian knapweed (Acroptilon repens (L.) DC.)

There are several factors thought to assist invasive weeds in colonization of ecosystems. One of these factors is allelopathy, the negative effect of chemicals produced by one plant on neighboring plants, frequently mediated through root exudates and other plant leachates. Acroptilon repens (Asteraceae) is one of the most invasive and ecologically threatening weed species in western North America. A bioassay-guided fractionation of the root extracts of this plant led to the isolation of five polyacetylenic compounds, of which one [5′-methoxy-1′-(5-prop-1-yn-1-yl-2-thienyl)-hexa-2′,4′-diyin-6′-yl acetate] was hitherto unknown. The structures of these compounds were elucidated on the basis of spectroscopic analysis (IR, ESIMS, ¹H, ¹³C NMR and 2D NMR). All of the compounds obtained, except 1-chloro-4-(5-penta-1,3-diyn-1-yl-2-thienyl)but-3-yn-2-ol, showed phytotoxic activity against Arabidopsis thaliana seedlings. The presence of 4′-chloro-1′-(5-penta-1,3-diyn-1-yl-2-thienyl)-but-2′-yn-3′-ol was detected in the root exudates of aeroponically grown A. repens plants. None of the polyacetylenes isolated in this study were found in Colorado soils collected between September 2006 and July 2007 in an A. repens colonized site. However, polyacetylene 5 in A. repens infested soil from Washington was found in June, 2007. Contrary to our previous report, the compound 7,8-benzoflavone (6) was not detected in root exudates, nor was it encountered in extracts of roots, aerial parts or infested soil. Since we could not repeat this work, the original report has been retracted [Stermitz, F.R., Bais, H.P., Foderaro, T.A., Vivanco, J.M., 2003. 7,8-Benzoflavone: a phytotoxin from root exudates of invasive Russian knapweed [A retraction]. Phytochemistry 64, 493-497.].     

Potential defense-related prenylated isoflavones in lactofen-induced soybean

An integrated LC-MS and NMR metabolomic study was conducted to investigate metabolites whose formation was induced by lactofen (1), a soybean (Glycine max L.) disease resistance-inducing herbicide. First, LC-MS analyses of control and lactofen (1)-induced soybean extracts were performed. The LC-MS raw data were then processed by a custom designed bioinformatics program to detect the induced metabolites so formed. Finally, structures of unknown induced metabolites were determined on the basis of their 1D and 2D NMR spectroscopic data. Structure of two previously unreported compounds, 7,8-dihydroxy-4′-methoxy-3′-prenylisoflavone (2) and 7-hydroxy-4′,8-dimethoxy-3′-prenylisoflavone (3) were elucidated together with four known prenylated compounds, 3′-prenyldaidzein (4), 8-prenyldaidzein (5), 3′-prenylgenistein (6), and 4-prenylcoumestrol (7). Compounds (2-6) are reported for the first time in soybean, as are the ¹³C chemical shift assignments for compound (7). Formation of these six prenylated compounds was also induced by the primary defense glucan elicitor from the cell wall of the pathogen Phytophthora sojae (Kauf. and Gerde.), further suggesting a potential role in soybean defense. These results highlight the metabolic flexibility within soybean secondary product pathways and suggest that prenylation may be associated with defense responses. Moreover, this study demonstrates a promising future approach using metabolomics on elicitor-induced plants for discovery of unknown compounds even in relatively well studied plants.     

Flavonoids and coumarins from Platymiscium praecox

The wood of Platymiscium praecox Mart. (Leguminosae-Lotoideae) contains sitosterol, 4,2′,4′-trihydroxychalcone, (2R)-7-hydroxyflavanone, (±)-7,4′-dihydroxyflavanone, (2S, 3S)-3,7-dihydroxyflavanone, 3,7-dihydroxyflavone, 3,7,4′-trihydroxyflavone, 6,7-dihydroxy-4′-methoxyisoflavone and 6,7-dimethoxycoumarin. It also contains three novel compounds: 7-hydroxy-4-methoxy-5-methylcoumarin, 7-O-glucosyloxy-4-methoxy-5-methylcoumarin and 7-hydroxy-4,8-dimethoxy-5-methylcoumarin.     

Four anti-protozoal and anti-bacterial compounds from Tapirira guianensis

Tapirira guianensis is a common tree used in traditional medicine in French Guiana against several infectious diseases (malaria, leishmaniasis, bacteria, etc.). The bioassay-guided purification of CH₂Cl₂ bark extract led to the isolation of four cyclic alkyl polyol derivatives: 4,6,2′-trihydroxy-6-[10′(Z)-heptadecenyl]-1-cyclohexen-2-one (1a), 1,4,6-trihydroxy-1,2′-epoxy-6-[10′(Z)-heptadecenyl]-2-cyclohexene (1b), 1,4,5,2′-tetrahydroxy-1-[10′(Z)-heptadecenyl]-2-cyclohexene (2), and 1,3,4,6-tetrahydroxy-1,2′-epoxy-6-[10′(Z)-heptadecenyl]-cyclohexane (3). The structures were established on the basis of 1D and 2D NMR analyses. The anti-leishmanial, anti-plasmodial, anti-bacterial (on Staphylococcus aureus, Staphylococcus epidermidis and Escherichia coli), and anti-fungal (on Candida albicans) activities of the extracts and of these original compounds were evaluated. Two showed medicinal interest supporting the traditional uses of the plant. The structures were established through spectral analyses of the isolates and their derivatives.     

Phenolic analogs of the N,C-coupled naphthylisoquinoline alkaloid ancistrocladinium A, from Ancistrocladus cochinchinensis (Ancistrocladaceae), with improved antiprotozoal activities

The first N,8′-coupled naphthylisoquinoline alkaloids with free phenolic OH groups, 4′-O-demethylancistrocladinium A and 6,4′-O-didemethylancistrocladinium A, have been isolated from the leaves and bark of the Vietnamese liana Ancistrocladus cochinchinensis, along with its known, non-phenolic parent compound, ancistrocladinium A, and four C,C-coupled representatives. The structure elucidation was achieved by chemical, spectroscopic, and chiroptical methods. The mono-phenolic alkaloid showed excellent activities in particular against the pathogen causing Chagas’ disease, Trypanosoma cruzi.     

Resistance of bioincised wood treated with wood preservatives to blue-stain and wood-decay fungi

Bioincising is a biotechnological process that aims at the improvement of wood preservative uptake in wood species with a low permeability, such as Norway spruce (Picea abies (L.) Karst). The process is based on a short-term pre-treatment with white-rot fungus Physisporinus vitreus. During incubation the membranes of bordered and half bordered pits are supposed to be degraded by fungal activity resulting in a better treatability of the wood structure for wood preservatives. In the present study, first of all the resistance of bioincised Norway spruce heartwood and untreated controls against blue-stain and wood-decay fungi (white- and brown-rot) was determined. Then, bioincised and untreated specimens were dipped or vacuum impregnated with six wood preservatives and substance uptake was assessed gravimetrically. Additionally, the penetration of 3-iodo-2-propynyl butylcarbamate (IPBC) into the wood was analyzed by high-pressure liquid chromatography (HPLC). Finally, wood resistance was assessed according to the European standards EN 152 and EN 113. Results showed no difference between bioincised wood without preservatives and the untreated wood against blue-stain discolouration. However, a significant (P < 0.05) increase in susceptibility against wood decay was recorded. In the bioincised wood samples a significantly higher uptake of all the different preservatives was determined and the HPLC-method revealed that IPBC penetrated deeper into bioincised wood than into control samples. The improved uptake of preservatives into bioincised wood resulted in a significantly higher resistance against white- and brown-rot fungi. However, only a slight protection against wood discolouration by blue-stain fungi was recorded. The results of this study show for the first time that the biotechnological process with P. vitreus can be used to improve wood durability by increasing the uptake and penetration of wood preservatives.