Biflavanoid proguibourtinidin carboxylic acids and their biflavanoid homologues from Acacia luederitzii

[4,6]- and [4,8]-Proguibourtinidin carboxylic acids (3,7,4′-trihydroxyl functionality) of 2,3-trans-3,4-trans: 2,3-cis- and 2,3-trans-3,4-trans: 2,3-trans-configuration based on (?)-epicatechin or (+)-catechin as constituent units, and their associated biflavanoid homologues, predominate in the heartwood of Acacia luederitzii. They are accompanied by stereochemical and functional analogues and by their putative flavan-3,4-diol and flavan-3-ol precursors.     

Synthesis and characterization of procyanidin dimers as their peracetates and octamethyl ether diacetates

Condensation of (2R,3S,4R or S)-leucocyanidin or the 5,7,3′,4′-tetramethyl ether of (2R,3^R,4S)-leucocyanidin with flavan-3-ols yielded dimeric flavanoids which were converted to their octamethyl ether diacetates, or the deca-acetates for the 2,3-trans-procyanadin series. Comparison is made of the ¹H NMR spectra of the deca-acetate and octamethyl ether diacetate derivatives which lead to useful diagnostic shift parameters characteristic of their structures. Condensations afforded a novel biflavanoid with a 3,4-cis-configuration and a triflavanoid of ‘mixed’ stereochemistry.     

Synthesis of biologically relevant biflavanoids--a review

Recent investigations show that naturally occurring biflavanoids possess anti-inflammatory, anticancer, antiviral, antimicrobial, vasorelaxant, and anticlotting activities. These activities have been discovered from the small number of biflavanoid structures that have been investigated, although the natural biflavanoid library is likely to be large. Structurally, biflavanoids are polyphenolic molecules comprised of two identical or non-identical flavanoid units conjoined in a symmetrical or unsymmetrical manner through an alkyl or an alkoxy-based linker of varying length. These possibilities introduce significant structural variation in biflavanoids, which is further amplified by the positions of functional groups--hydroxy, methoxy, keto, or double bond--and stereogenic centers on the flavanoid scaffold. In combination, the class of biflavanoids represents a library of structurally diverse molecules, which remains to be fully exploited. Since the time of their discovery, several chemical approaches utilizing coupling and rearrangement strategies have been developed to synthesize biflavanoids. This review compiles these synthetic approaches into nine different methods including Ullmann coupling of halogenated flavones, biphenyl-based construction of biflavanoids, metal-catalyzed cross-coupling of flavones, Wessely-Moser rearrangements, oxidative coupling of flavones, Ullmann condensation with nucleophiles, nucleophilic substitutions for alkoxy biflavanoids, and dehydrogenation-based or hydrogenation-based synthesis. Newer, more robust synthetic approaches are necessary to realize the full potential of the structurally diverse class of biflavanoids.     

Biflavanoids of the Cycadales

Biflavanoid patterns of leaves of 82 species of the order Cycadales comprising 3 families and 10 genera have been determined. The biflavanoids were identified by TLC, UV, NMR and MS studies. Pattern differences between species, when detected, involve the position or degree of methylation of the base compounds. On the other hand, differences in the biflavanoid patterns at the generic and family levels were sufficient to support taxonomic relationships. Thus, the absence of hinokiflavone and its derivatives clearly distinguish the Zamiaceae from the Cycadaceae and Stangeriaceae. The complete absence of biflavanoids in the latter family suggests an advanced evolutionary condition, but morphologically, this family has the most fern-like characters, and therefore has been considered by previous workers to be the most primitive of the cycads.     

Secondary metabolites from Eurotium species, Aspergillus calidoustus and A. insuetus common in Canadian homes with a review of their chemistry and biological activities

As part of studies of metabolites from fungi common in the built environment in Canadian homes, we investigated metabolites from strains of three Eurotium species, namely E. herbariorum, E. amstelodami, and E. rubrum as well as a number of isolates provisionally identified as Aspergillus ustus. The latter have been recently assigned as the new species A. insuetus and A. calidoustus. E. amstelodami produced neoechinulin A and neoechinulin B, epiheveadride, flavoglaucin, auroglaucin, and isotetrahydroauroglaucin as major metabolites. Minor metabolites included echinulin, preechinulin and neoechinulin E. E. rubrum produced all of these metabolites, but epiheveadride was detected as a minor metabolite. E. herbariorum produced cladosporin as a major metabolite, in addition to those found in E. amstelodami. This species also produced questin and neoechinulin E as minor metabolites. This is the first report of epiheveadride occurring as a natural product, and the first nonadride isolated from Eurotium species. Unlike strains from mainly infection-related samples, largely from Europe, neither ophiobolins G and H nor austins were detected in the Canadian strains of A. insuetus and A. calidoustus tested, all of which had been reported from the latter species. TMC-120 A, B, C and a sesquiterpene drimane are reported with certainty for the first time from indoor isolates, as well as two novel related methyl isoquinoline alkaloids.     

Identification of a Bifunctional Maize C- and O-Glucosyltransferase

Flavonoids accumulate in plant vacuoles usually as O-glycosylated derivatives, but several species can also synthesize flavonoid C-glycosides. Recently, we demonstrated that a flavanone 2-hydroxylase (ZmF2H1, CYP93G5) converts flavanones to the corresponding 2-hydroxy derivatives, which are expected to serve as substrates for C-glycosylation. Here, we isolated a cDNA encoding a UDP-dependent glycosyltransferase (UGT708A6), and its activity was characterized by in vitro and in vivo bioconversion assays. In vitro assays using 2-hydroxyflavanones as substrates and in vivo activity assays in yeast co-expressing ZmF2H1 and UGT708A6 show the formation of the flavones C-glycosides. UGT708A6 can also O-glycosylate flavanones in bioconversion assays in Escherichia coli as well as by in vitro assays with the purified recombinant protein. Thus, UGT708A6 is a bifunctional glycosyltransferase that can produce both C- and O-glycosidated flavonoids, a property not previously described for any other glycosyltransferase.     

Evaluation of Nostoc Strain ATCC 53789 as a Potential Source of Natural Pesticides

The cyanobacterium Nostoc strain ATCC 53789, a known cryptophycin producer, was tested for its potential as a source of natural pesticides. The antibacterial, antifungal, insecticidal, nematocidal, and cytotoxic activities of methanolic extracts of the cyanobacterium were evaluated. Among the target organisms, nine fungi (Armillaria sp., Fusarium oxysporum f. sp. melonis, Penicillium expansum, Phytophthora cambivora, P. cinnamomi, Rhizoctonia solani, Rosellinia, sp., Sclerotinia sclerotiorum, and Verticillium albo-atrum) were growth inhibited and one insect (Helicoverpa armigera) was killed by the extract, as well as the two model organisms for nematocidal (Caenorhabditis elegans) and cytotoxic (Artemia salina) activity. No antibacterial activity was detected. The antifungal activity against S. sclerotiorum was further studied with both extracts and biomass of the cyanobacterium in a system involving tomato as a host plant. Finally, the herbicidal activity of Nostoc strain ATCC 53789 was evaluated against a grass mixture. To fully exploit the potential of this cyanobacterium in agriculture as a source of pesticides, suitable application methods to overcome its toxicity toward plants and nontarget organisms must be developed.     

A re-evaluation ofBlayacina Cobbold 1932 andThoralaspis Hupe 1953 (Trilobita: Redlichiida)

The monotypic trilobite generaBlayacina andThoralaspis from the late Early Cambrian of the Montagne Noire, Southern France, are revised. Restudy of the type specimens and of new material from the type locality and stratum as well as morphometric measurements strongly support the assumption that both taxa are identical and that morphologic as well as taxonomic differences resulted from tectonic distortion. Thus,Thoralaspis thorali has to be regarded as a subjective junior synonym ofBlayacina miqueli andThoralaspis as a junior synonym ofBlayacina. Its systematic position as a morphologic group aroundLusatiops within the Ellipsocephalidae-Protoleninae is confirmed.     

Vulnerability of Pathogenic Biofilms to Micavibrio aeruginosavorus

The host specificity of the gram-negative exoparasitic predatory bacterium Micavibrio aeruginosavorus was examined. M. aeruginosavorus preyed on Pseudomonas aeruginosa, as previously reported, as well as Burkholderia cepacia, Klebsiella pneumoniae, and numerous clinical isolates of these species. In a static assay, a reduction in biofilm biomass was observed as early as 3 hours after exposure to M. aeruginosavorus, and an ~100-fold reduction in biofilm cell viability was detected following a 24-h exposure to the predator. We observed that an initial titer of Micavibrio as low as 10 PFU/well or a time of exposure to the predator as short as 30 min was sufficient to reduce a P. aeruginosa biofilm. The ability of Micavibrio to reduce an existing biofilm was confirmed by scanning electron microscopy. In static and flow cell experiments, M. aeruginosavorus was able to modify the overall P. aeruginosa biofilm structure and markedly decreased the viability of P. aeruginosa. The altered biofilm structure was likely caused by an increase in cell-cell interactions brought about by the presence of the predator or active predation. We also conducted a screen to identify genes important for P. aeruginosa-Micavibrio interaction, but no candidates were isolated among the ~10,000 mutants tested.     

Effects of Plasmodium gallinaceum on hemolymph physiology of Aedes aegypti during parasite development

Insect disease vectors show diminished fecundity when infected with Plasmodium. This phenomenon has already been demonstrated in laboratory models such as Aedes aegypti, Anopheles gambiae and Anopheles stephensi. This study demonstrates several changes in physiological processes of A. aegypti occurring upon infection with Plasmodium gallinaceum, such as reduced ecdysteroid levels in hemolymph as well as altered expression patterns for genes involved in vitellogenesis, lipid transport and immune response. Furthermore, we could show that P. gallinaceum infected A. aegypti presented a reduction in reproductive fitness, accompanied by an activated innate immune response and increase in lipophorin expression, with the latter possibly representing a nutritional resource for Plasmodium sporozoites.     

Three new species of woodlizards (Hoplocercinae,Enyalioides) from northwestern South America

The discovery of three new species of Enyalioides from the tropical Andes in Ecuador and northern Peru is reported. Enyalioides altotambo sp. n. occurs in northwestern Ecuador and differs from other species of Enyalioides in having dorsal scales that are both smooth and homogeneous in size, a brown iris, and in lacking enlarged, circular and keeled scales on the flanks. Enyalioides anisolepis sp. n. occurs on the Amazonian slopes of the Andes in southern Ecuador and northern Peru and can be distinguished from other species of Enyalioides by its scattered, projecting large scales on the dorsum, flanks, and hind limbs, as well as a well-developed vertebral crest, with the vertebrals on the neck at least three times higher than those between the hind limbs. Enyalioides sophiarothschildae sp. n. is from the Amazonian slopes of the Cordillera Central in northeastern Peru; it differs from other species of Enyalioides in having caudal scales that are relatively homogeneous in size on each caudal segment, a white gular region with a black medial patch and several turquoise scales in males, as well as immaculate white labials and chin. A molecular phylogenetic tree of 18 species of hoplocercines is presented, including the three species described in this paper and Enyalioides cofanorum, as well as an updated identification key for species of Hoplocercinae.     

Plantamajoside — A current review

Plantamajoside is a bioactive caffeic acid derivative, a dihydroxyphenethyl glucoside in the group of polyphenolic compounds. It is one of the principal caffeic acid glycoside in the Plantago Digitalis, Hemiphragma, Lagotis, Picrorhiza, Rehmannia, Veronica, Wulfeniopsis and Wulfenia genera within the Plantaginaceae family. This compound is also present in the genera Aeschynanthus and Chirita of the Gesneriaceae family and the genus Boschniakia of the Orobanchaceae family. Plantamajoside is present in the greatest concentrations in roots of young plants, but it is also found in seeds, flower stalks, stems, leaves, in vivo cultivated plant cells and transgenic root cultures. Plantamajoside is used as a biomarker in chemotaxonomical studies, and is a compound with numerous biological applications and considerable pharmacological potential. It is a protective agent against ultra-violet light in plants and acts as antioxidant agent with very low toxicity. In addition, plantamajoside can also be industrially synthesized. This review aims to give an overview of plantamajoside in various plantago species as well as its potential as a biomarker and as a new drug compound.     

Mondia whitei (Apocynaceae): A review of its biological activities, conservation strategies and economic potential

Globally, the commercialisation of plants as observed in their uses by many industries such as the cosmeceutical, nutraceutical and pharmaceutical ones is gaining more interest and popularity. Mondia whitei is a popular medicinal plant which is endemic to Africa. Since antiquity, M. whitei has been used by African people to treat various ailments. The roots were used for the treatment of anorexia, stress, bilharzia and sexual dysfunction as well as for general aches and pains. Researchers have evaluated the efficacy of most of these claims by screening the M. whitei for biological activities such as antimicrobial, anti-inflammatory and anthelmintic as well as aphrodisiac efficacy. Furthermore, M. whitei has horticultural, nutritional and other socio-cultural values as reported in countries such as South Africa, Nigeria, Zimbabwe, Kenya, Uganda and Malawi. As a result of its numerous uses across the African continent, we attempt to explore and assess the economic potential of M. whitei with emphasis on medicinal values. The root of M. whitei is the most popular organ used in traditional medicine; consequently, this has resulted in the species becoming rare or threatened with extinction in the wild. Several authors have suggested solutions such as plant or plant part substitution to overcome the over-harvesting problem. The application of biotechnology techniques such as micropropagation and hairy roots also remain viable options which are presently being utilised to a lesser extent. Nevertheless, the sustainable harvesting and feasible conservation strategy for the species remains a major challenge. It is strongly recommended that in as much as the economic potential of M. whitei should be exploited, more detailed attention and studies should be geared towards its conservation. In order to ensure sustainable use and to derive maximum economic benefits, it is necessary to have empirical information detailing its ethno-botanical values, conservation status and commercial potential.     

Four new species and a new record of Orchidinae (Orchidaceae: Orchideae) from China

Four new species of Orchidaceae from China, Heminium lijiangense, Peristylus fasciculatus, Platanthera milinensis, and Ponerorchis gongshanensis, together with a new country record, Peristylus tenuicallus, are described and illustrated based on morphological and/or phylogenetic analyses. Heminium lijiangense is closely related to H. elisabethae but differs from it by having the dorsal sepal ovate-orbicular and lip mid-lobe distinctly shorter than lateral lobes. P. fasciculatus is close to Peristylus tradescantifolius but is distinguished from it by having several fascicled and straight, root-like tubers (vs. one or two oblongoid tubers), old stems usually persistent, middle lobe of lip narrowly ligulate-lanceolate and half as long as the lateral lobes (vs. middle lobe deltoid, about a third as long as the lateral lobes or less), a raised callus at the base of each lateral lobe (vs. callus absent), spur gradually attenuate toward the apex (vs. spur clavate). Platanthera milinensis is similar to P. stenochila by sharing small green flowers and lip without a spur, but differs in having a creeping rhizome, a corymbose inflorescence, and a broadly ovate and slightly 3-lobed lip. Ponerochis gongshanensis is similar to P. faberi in its small flowers, but differs in having a linear leaf c. 3 mm wide (vs. leaf 5–13 mm wide), in the lip having collar-like raised margins on the sides of the spur entrance, and a mid-lobe which is notched at the apex but not divided into two divergent lobules that are nearly as large as the lateral lobes, as in P. faberi. All the proposed species obtained high support in phylogenetic analysis as new species. The recently described genus Apetalanthe is reduced to synonymy of Ponerorchis and a new combination is made.     

Preparation of chlorophyll a, chlorophyll b and bacteriochlorophyll a by means of column chromatography with diethylaminoethylcellulose

Chlorophyll a, chlorophyll b and bacteriochlorophyll a were prepared by means of column chromatography with Sephadex LH-20 and diethylaminoethylcellulose. This method provides purified preparations of chlorophylls in about 3 h.To prepare chlorophyll a, blue-green or red algae were used as the starting material. Chlorophyll a was extracted with 90% aqueous acetone from cells of blue-green algae, Anabaena variabilis, Anacystis nidulans and Tolypothrix tenuis, and with 90% aqueous methanol from thalli of a red alga, Porphyra yezoensis. Chlorophyll a was collected as precipitates by adding dioxane and water to the extract according to the method of Iriyama et al. [6]. The crude chlorophyll a preparation was applied to a Sephadex LH-20 column with chloroform as the eluent and then to a DEAE-cellulose column with a chloroform/methanol mixture (49 : 1, v/v) as the eluent. Analysis with thin layer chromatography revealed that the chlorophyll a preparation contained no detectable contaminants.Bacteriochlorophyll a was prepared in a similar manner from purple photosynthetic bacteria, Rhodopseudomonas spheroides and Chromatium vinosum.In order to prepare chlorophyll b, chloroplasts of spinach leaves were used as the starting material. A mixture of chlorophylls a and b was obtained in the same way as described for the preparation of chlorophyll a from the blue-green algae. To separate chlorophyll b from chlorophyll a, the mixture was applied to a diethylaminoethylcellulose column which was developed with a hexane/2-propanol mixture (5 : 2, v/v).     

Influence of Nonhost Plants on Population Decline of Rotylenchulus reniformis

The influence of Chloris gayana, Crotalaria juncea, Digitaria decumbens, Tagetes patula, and a chitin-based soil amendment on Hawaiian populations of Rotylenchulus reniformis was examined. Chloris gayana was a nonhost for R. reniformis. The nematode did not penetrate the roots, and in greenhouse and field experiments, C. gayana reduced reniform nematode numbers at least as well as fallow. Tagetes patula was a poor host for reniform nematode and reduced reniform nematode numbers in soil better than did fallow. Crotalaria juncea was a poor host for R. reniformis, and only a small fraction of the nematode population penetrated the roots. Crotalaria juncea and D. decumbens reduced reniform nematode populations at least as well as fallow. A chitin-based soil amendment, applied at 2.24 t/ha to fallow soil, did not affect the population decline of reniform nematode.     

Description of a new species of Petrolisthes in the Indo-West Pacific with a redefinition of P. hastatus Stimpson, 1858 and resurrection of P. inermis (Heller, 1862) (Crustacea,Anomura, Porcellanidae)

The porcellanid crab Petrolisthes hastatus Stimpson, 1858, has been traditionally viewed as a highly variable species with a wide distribution in the West Pacific. For more than a century there has been taxonomic confusion of this species with morphologically similar taxa, some of which were synonymized with Stimpson’s taxon. We redefine Petrolisthes hastatus, resurrect Petrolisthes inermis as a valid species, discuss the status of Petrolisthes tenkatei De Man, 1893, and describe a new species as Petrolisthes elegantissimus from Indonesia.     

Recent findings in evolution and function of insect innexins

The past decade has seen significant advances in the field of innexin biology, particularly in the model invertebrate organisms, the nematode Caenorhabditis elegans and the fly Drosophila melanogaster. However, advances in genomics and functional techniques during this same period are ushering in a period of comparative innexin biology. Insects are the most diverse metazoan taxa in terms of species number, as well as in developmental, physiological, and morphological processes. Combined with genomics data, the study of innexins should rapidly advance. In this review, we consider the current state of knowledge regarding innexins in insects, focusing on innexin diversity, both evolutionary and functional. We also consider an unusual set of innexins, known as vinnexins, that have been isolated from mutualistic viruses of some parasitoid wasps. We conclude with a call to study insect innexins from a broader, evolutionary perspective. Knowledge derived from such comparative studies will offer significant insight into developmental and evolutionary physiology, as well as specific functional processes in a taxon that has huge biomedical and ecological impact on humans.