Use of chiral auxiliaries in the asymmetric synthesis of biologically active compounds: A review

This review article describes the use of some of the most popular chiral auxiliaries in the asymmetric synthesis of biologically active compounds. Chiral auxiliaries derived from naturally occurring compounds, such as amino acids, carbohydrates, and terpenes, are considered essential tools for the construction of highly complex molecules. We highlight the auxiliaries of Evans, Corey, Yamada, Enders, Oppolzer, and Kunz, which led to remarkable progress in asymmetric synthesis in the last decades and continue to bring advances until the present day.     

Molecular mapping in tropical maize (Zea mays L.) using microsatellite markers. 1. Map construction and localization of loci showing distorted segregation

Microsatellites have become the most important class of markers for mapping procedures. Primarily based on restriction fragment length polymorphism (RFLP) markers, several molecular genetic maps of maize have been developed, mainly using temperate inbred maize lines. To characterize the level of polymorphism of microsatellite loci and construct a genetic map in tropical maize, two elite inbred lines, L-08-05F and L-14-4B, were crossed to produce 400 F(2) individuals that were used as a mapping population. A survey of 859 primer pair sequences of microsatellites was used. The polymorphism screens of each microsatellite and genotype assignment were performed using high-resolution agarose gels. About 54 % of the primer sets gave clearly scorable amplification products, 13 % did not amplify and 33 % could not be scored on agarose gels. A total of 213 polymorphic markers were identified and used to genotype the mapping population. Among the polymorphic markers, 40 showed loci deviating from expected Mendelian ratios and clusters of deviating markers were located in three chromosome regions. Non-Mendelian scoring was present in 19 markers. The final genetic map with 117 markers spanned 1634 cM in length with an average interval of 14 cM between adjacent markers.     

Measurement on Camber Deformation of Wings of Free-flying Dragonflies and Beating-flying Dragonflies

1　IntroductionNumerouskinematicparameters,includingwing beatfrequency ,wingorientation ,andbothspan andchord wisedeformation ,arerelevanttotheaerodynam icanalysisofinsectflight[1,2 ] .Althoughnearlyalltherecentstudiesofinsectflightaerodynamics[3,4 ] haveidentifiedthatthemechanismsrequireflowseparationattheleadingedge ,andcamberisnotexpectedtohaveanysignificantinfluenceonthemagnitudeoftheforcecoefficient,someinsects ,suchasdragonfliesandbut terflies,frequently glideusinglowanglesofattack ,lead…     

Leptin induces macrophage lipid body formation by a phosphatidylinositol 3-kinase- and mammalian target of rapamycin-dependent mechanism

Leptin is an adipocyte-derived hormone/cytokine that links nutritional status with neuroendocrine and immune functions. Lipid bodies (lipid droplets) are emerging as dynamic organelles with roles in lipid metabolism and inflammation. Here we investigated the roles of leptin in signaling pathways involved in cytoplasmic lipid body biogenesis and leukotriene B(4) synthesis in macrophages. Our results demonstrated that leptin directly activated macrophages and induced the formation of adipose differentiation-related protein-enriched lipid bodies. Newly formed lipid bodies were sites of 5-lipoxygenase localization and correlated with an enhanced capacity of leukotriene B(4) production. We demonstrated that leptin-induced macrophage activation was dependent on phosphatidylinositol 3-kinase (PI3K) activity, since the lipid body formation was inhibited by LY294002 and was absent in the PI3K knock-out mice. Leptin induces phosphorylation of p70(S6K) and 4EBP1 key downstream signaling intermediates of the mammalian target of rapamycin (mTOR) pathway in a rapamycin-sensitive mechanism. The mTOR inhibitor, rapamycin, inhibited leptin-induced lipid body formation, both in vivo and in vitro. In addition, rapamycin inhibited leptin-induced adipose differentiation-related protein accumulation in macrophages and lipid body-dependent leukotriene synthesis, demonstrating a key role for mTOR in lipid body biogenesis and function. Our results establish PI3K/mTOR as an important signaling pathway for leptin-induced cytoplasmic lipid body biogenesis and adipose differentiation-related protein accumulation. Furthermore, we demonstrate a previously unrecognized link between intracellular (mTOR) and systemic (leptin) nutrient sensors in macrophage lipid metabolism. Leptin-induced increased formation of cytoplasmic lipid bodies and enhanced inflammatory mediator production in macrophages may have implications for obesity-related cardiovascular diseases.     

Molecular evolution of olfactomedin

Olfactomedin is a secreted polymeric glycoprotein of unknown function, originally discovered at the mucociliary surface of the amphibian olfactory neuroepithelium and subsequently found throughout the mammalian brain. As a first step toward elucidating the function of olfactomedin, its phylogenetic history was examined to identify conserved structural motifs. Such conserved motifs may have functional significance and provide targets for future mutagenesis studies aimed at establishing the function of this protein. Previous studies revealed 33% amino acid sequence identity between rat and frog olfactomedins in their carboxyl terminal segments. Further analysis, however, reveals more extensive homologies throughout the molecule. Despite significant sequence divergence, cysteines essential for homopolymer formation such as the CXC motif near the amino terminus are conserved, as is the characteristic glycosylation pattern, suggesting that these posttranslational modifications are essential for function. Furthermore, evolutionary analysis of a region of 53 amino acids of fish, frog, rat, mouse, and human olfactomedins indicates that an ancestral olfactomedin gene arose before the evolution of terrestrial vertebrates and evolved independently in teleost, amphibian, and mammalian lineages. Indeed, a distant olfactomedin homolog was identified in Caenorhabditis elegans. Although the amino acid sequence of this invertebrate protein is longer and highly divergent compared with its vertebrate homologs, the protein from C. elegans shows remarkable similarities in terms of conserved motifs and posttranslational modification sites. Six universally conserved motifs were identified, and five of these are clustered in the carboxyl terminal half of the protein. Sequence comparisons indicate that evolution of the N-terminal half of the molecule involved extensive insertions and deletions; the C-terminal segment evolved mostly through point mutations, at least during vertebrate evolution. The widespread occurrence of olfactomedin among vertebrates and invertebrates underscores the notion that this protein has a function of universal importance. Furthermore, extensive modification of its N-terminal half and the acquisition of a C-terminal SDEL endoplasmic-reticulum- targeting sequence may have enabled olfactomedin to adopt new functions in the mammalian central nervous system.      

Benzyltetrahydroisoquinoline-derived alkaloids as systematic markers

Basic unsubstituted skeleta within biogenetic groups can be codified according to their position along biosynthetic pathways aligned in order of probability of occurrence. Correlation of the codified structural type with the taxa in which they are found is effected through frequency indices associated with the relative number of derivatives of the skeleton in the taxon and the relative number of subunits of the taxon which contain derivatives thereof. The benzyltetrahydroisoquinolines, a biogenetically related group of compounds, serves as example of the applicability of the method, which is part of an integrated system of expression of biochemical data in biological systematics.     

Host plant intraspecific variation determines gall traits

• Galls display a multiplicity of traits, including colours, which are driven by pigment accumulation. Their conspicuousness has attracted researchers' attention and several hypotheses have been raised. However, plants themselves vary intra-specifically, including in their pigment concentrations. As galls are a result of host tissue development, colours may be a by-product of the host's own traits, being more conspicuous simply because the sites where galls develop already have the predisposition to accumulate more pigment. Here, we call this the host variation hypothesis.
• We test this hypothesis using the system of galls induced by Palaeomystella oligophaga on Macairea radula host plant. Using spectrophotometry, we calculated the Anthocyanin Reflectance Index (ARI) of gall projections, which are responsible for their characteristic colours. We tested the influence of occupant identity (galling insect or any natural enemy), gall volume, parenchyma thickness, height from the ground, ARI of leaf, ARI of gall surface and ARI of the respective stem.
• We corroborated the host variation hypothesis since the anthocyanin content in stems and in galls' projections were positively related. Moreover, anthocyanin in galls' projections was positively related to anthocyanin in the gall surface and negatively related to gall volume and parenchyma thickness. This shows that, besides the host specificities, galls' own traits may also be responsible for pigment accumulation, influencing their colours.
• In this study, using colour as an example, we show that although galls tend to be considered complex expressions of galling insects' stimuli, their traits may be simply influenced by previous and specific attributes of the host organs.

     

Xanthones as systematic markers

An evolutionary scheme for shikimate-acetate derived xanthones is deduced from their substitution pattern. Increasing distance of a particular xanthone from the primitive precursor is symbolized by increasing numbers. Each xanthone containing plant species is characterized by the average of the numbers attributed to its constituents. Each genus is characterized by the average of the numbers calculated for its species. The method is useful in comparing phyletic order of genera within the Guttiferae.     

Accumulation of few-polyhedra mutants upon serial passage of Anticarsia gemmatalis multiple nucleopolyhedrovirus in cell culture

Anticarsia gemmatalis nucleopolyhedrovirus (AgMNPV) has been widely used to control the velvetbean caterpillar, Anticarsia gemmatalis, in Brazil. To date, AgMNPV has been produced by larval infection and, due to in vivo production limitations and the continuing high demand for the biopesticide, attempts should be made to develop in vitro production of this virus. In order to investigate the effects caused by serial passage of AgMNPV in cell culture, we carried out a total of ten passages and analyzed the morphological and the genomic changes of the virus. After six passages, the many-polyhedra (MP) phenotype started to switch to the few-polyhedra (FP) phenotype which rapidly accumulated in the virus population. Ultrastructural analysis showed typical signs of FP mutant formation such as decrease in the number of polyhedra per cell, polyhedra aberrant morphology and low numbers of virions occluded in the protein matrix. Also enhanced BV production was observed from the fifth passage indicating that FP mutants were becoming predominant in comparison to the wild type virus. Restriction endonuclease analysis of the viral DNA revealed that lower and higher passages had similar profiles indicating that there were no large insertions or deletions or rearrangements in their genomes and indicating the generation of FP mutants instead of defective interfering viruses.     

Effects of phenotypic complementarity and phylogeny on the nested structure of mutualistic networks

Recent studies have started to unravel the structure of mutualistic networks, although few functional explanations underlying such structure have been explored. We used computer simulations to test whether complementarity between phenotypic traits of plants and animals can explain the pervasive tendency of specialists to interact with proper subsets of species that generalists interact with (nested interactions), and how phylogeny affects such interaction patterns. Simultaneously, we assessed whether complementarity and phylogenetic structure were associated with patterns of interaction in a real mutualistic community. Simulation results support that highly nested networks can emerge from phenotypic complementarity, particularly when several traits are involved. The hierarchical structure of phylogenetic relations can also contribute to increased nestedness because traits determining complementarity are then inherited in a correlated fashion. Phylogenetic effects on resulting generalization levels are often low, but can be detected. Results from the empirical network support a relevant role of complementarity and phylogenetic history on interaction patterns. Our results demonstrate that these factors can contribute to nestedness, which emphasize the necessity of considering evolutionary mechanisms in studies of community structure.