RESUMEN
A highly chemoselective [2+1] annulation of α-alkylidene pyrazolones with α-bromonitroalkenes has been achieved under mild conditions. α-Alkylidene pyrazolones were unprecedentedly used as a C1 synthon to participate in annulation reactions, providing access to diverse vinylcyclopropane-based pyrazolone products. In addition, a spectrum of pharmaceutically interesting pyrazole-fused pyranone oximes could be rapidly obtained through a [2+1] annulation/rearrangement sequential process. Computational studies disclosed the origin of the observed chemoselectivity of the [2+1] cycloaddition.
RESUMEN
An asymmetric catalytic multicomponent reaction of malononitrile, benzaldehyde, and α-arylidene pyrazolinones to produce spiropyrazolones has been reported. The [1 + 2 + 3] multicomponent reaction was catalyzed by chiral cinchona alkaloids to provide spiropyrazolones in high yields, with excellent enantioselectivities and good diastereoselectivities. We also performed control experiments and proposed a plausible catalytic cycle based on the observed experimental results to explain the reaction process and stereoselectivity of the asymmetric multicomponent reaction.
RESUMEN
A chemoselective cross Rauhut-Currier-type reaction has been developed involving a tri-substituted alkene (trifluoromethyl-containing acrylonitrile derivative) with a di- or tri-substituted alkene to yield tetra-substituted double bonds in RC-type products. This approach can support the synthesis of trifluoromethylated tetra-substituted olefins and synthetically important, structurally complex 3-allylic-type oxindole skeletons. The asymmetric version of this RC-type reaction can be realized by combining a Brønsted acid and Lewis base for bifunctional H-bonding-tertiary amine catalysis. Subsequent transformation of multi-functionalized RC-type product leads to pharmacologically interesting cyclohexane-based spiro-pyrazolones bearing six contiguous chiral centers and two highly congested, vicinal quaternary carbon centers.
RESUMEN
Based on an efficient sample clean-up and field-amplified sample injection online preconcentration technique in capillary electrophoresis with contactless conductivity detection, a new analytical method for the sensitive determination of melamine in milk samples was established. In order to remove the complex matrix interference, which resulted in a serious problem during field-amplified sample injection, liquid-liquid extraction was utilized. As a result, liquid-liquid extraction provides excellent sample clean-up efficiency when ethyl acetate was used as organic extraction by adjusting the pH of the sample solution to 9.5. Both inorganic salts and biological macromolecules are effectively removed by liquid-liquid extraction. The sample clean-up procedure, capillary electrophoresis separation parameters and field-amplified sample injection conditions are discussed in detail. The capillary electrophoresis separation was achieved within 5 min under the following conditions: an uncoated fused-silica capillary, 12 mM HAc + 10 mM NaAc (pH = 4.6) as running buffer, separation voltage of +13 kV, electrokinetic injection of +12 kV × 10 s. Preliminary validation of the method performance with spiked melamine provided recoveries >90%, with limits of detection and quantification of 0.015 and 0.050 mg/kg, respectively. The relative standard deviations of intra- and inter-day were below 6%. This newly developed method is sensitive and cost effective, therefore, suitable for screening of melamine contamination in milk products.
RESUMEN
Neotyphodium species evolved from Epichloë species and are asexual, seedborne endophytes in many cool-season grasses. Here we propose a new species inhabiting Festuca parvigluma native to China. Morphology, host specificity and molecular phylogenetic evidence supported recognition of this new species. Sequences of beta-tubulin gene (tubB) introns and translation elongation factor 1-alpha gene (tefA) introns were present as two copies in all five isolates examined. In phylogenetic analyses copy 1 was closely related to E. yangzii in the EBY clade and copy 2 with E. typhina in the ETC clade, indicating this new species might have originated as a result of hybridization between members of these two clades. Referring to the distribution area of host plants, Neotyphodium sinofestucae is proposed for this new species.
Asunto(s)
Festuca/microbiología , Neotyphodium/clasificación , Filogenia , China , Epichloe/genética , Hibridación Genética , Intrones/genética , Neotyphodium/genética , Neotyphodium/aislamiento & purificación , Neotyphodium/ultraestructura , Factor 1 de Elongación Peptídica/genética , Análisis de Secuencia de ADN , Especificidad de la Especie , Tubulina (Proteína)/genéticaRESUMEN
We describe a new stromata-producing Neotyphodium species symbiotic with clonal Calamagrostis epigeios (L.) Roth. Stromata on the grass, 47.5-186 mm long, occurred frequently, but neither perithecium nor mature ascus was observed. Morphology of fungal isolates obtained from symptomatic and asymptomatic tillers were identical to each other and similar to those of epichloë endophytes. In phylogenetic analysis all selected five fungal isolates clustered into a significantly distinct clade based on sequences of beta-tubulin gene (tubB) introns and translation elongation factor 1-alpha gene (tefA) introns with bootstrap values of 99%, supporting erection of a new species. Concerning the production of extremely long stromata on the host plants and absence of sexual spores, we propose the name Neotyphodium stromatolongum Y. Ji, L. Zhan et Z. Wang, sp. nov.
Asunto(s)
Neotyphodium/clasificación , Neotyphodium/fisiología , Poaceae/microbiología , China , Neotyphodium/citología , Neotyphodium/aislamiento & purificación , Filogenia , Poaceae/crecimiento & desarrollo , Especificidad de la Especie , Simbiosis/fisiologíaRESUMEN
Epichloë species are fungal symbionts (endophytes) of grasses, six European and four North American biological species in genus Epichloë have been described in previous researches. In this study we describe a new Epichloë species, Epichloë yangzii Li et Wang, found in natural symbioses with Roegneria kamoji native to China. We investigated the host specificity, morphology, interfertility tests and molecular phylogenetic evidences of this new species. The results indicated that E. yangzii is host specific and seedborne. Most morphological characteristics of this new species are typical in the genus. However differences are evident in several features including size of perithecia, asci and ascospores. In mating tests E. yangzii was not interfertile with E. elymi isolates from related hosts in genera Elymus. Phylogenetic relationships based on sequences of beta-tubulin gene (tub2) introns and translation elongation factor 1-alpha gene (tef1) introns showed that members of the new species grouped into exclusive clades with high bootstrap value.